WO2011103940A1 - Carboxyl-functionalized silicon-containing precursor compound of various organic carboxylic acids - Google Patents

Abstract

The invention relates to a composition of a carboxyl-functionalized silicon-containing precursor compound of at least two different organic acids, said composition having two, three, or four carboxyl groups functionalized with various hydrocarbon groups according to formula I and/or II. Said carboxyl groups can be released as carboxylic acids and can be used as silane hydrolysis catalysts and/or silane condensation catalysts. The invention further relates to methods for producing the composition, to the use of the composition for cross-linking polymers, and to a formulation of the composition in the form of a masterbatch.

Description

Carboxy-functionalized silicon-containing precursor compound of various organic carboxylic acids

The invention relates to a composition of a carboxy-functionalized, silicon-containing precursor compound of at least two different organic acids which has two, three or four hydrocarbon radicals functionalized carboxy groups according to formula I and / or II which are released as carboxylic acids and Silanhydrolyse- catalyst and / or silane condensation catalyst can be used. Furthermore, the invention relates to processes for their preparation, their use for crosslinking of

Polymers, as well as a formulation of these in the form of a masterbatch.

For the preparation of filled and unfilled polymer compounds, in particular of polyethylene (PE) and its copolymers, it is known to crosslink silane-grafted or silane-co-polymerized polyethylenes as silanol condensation catalysts, organotin compounds or aromatic sulphonic acids (Borealis Ambicat ®). A disadvantage of the organotin compounds is their

Significant toxicity, while the sulphonic acids are noticeable by their pungent odor, which continues through all process stages to the final product. By

reaction-related by-products, the polymer compounds crosslinked with sulphonic acids are generally unsuitable for use in the food sector or in the field of drinking water supply, for example for the production of

Drinking water pipes. Usual tin

Silanol condensation catalysts are dibutyltin dilaurate (dibutyltindilaurate, DBTDL) and dioctyltin dilaurate (dioctyltindilaurate, DOTL), which act as a catalyst via their coordination sphere.

It is known for the preparation of moisture-crosslinkable polymers silanes in the presence of radical formers on

Graft polymer chains and after shaping the

Moisture crosslinking in the presence of said

Silanhydrolysekatalysatoren and / or silanol condensation catalysts perform. The moisture crosslinking of polymers with hydrolyzable unsaturated silanes is used worldwide for the production of cables, pipes, foams, etc. Processes of this type are known under the name Sioplas process (DE 19 63 571 C3, DE 21 51 270 C3, US 3,646,155) and monosil process (DE 25 54 525 C3, US 4,117,195).

While in the monosil process the crosslinking catalyst is already added during the first processing step, in the Sioplas process the addition of the crosslinking catalyst takes place only in the subsequent, the shaping step. In addition, vinyl-functional silanes can be used together with the

Monomers and / or prepolymers are copolymerized directly to the base polymer or coupled to polymers via grafting to the polymer chains.

EP 207627 discloses further tin-containing catalyst systems ^¬ and thus modified co-polymers based on the reaction of dibutyltin oxide with ethylene-acrylic acid co-polymers. JP 58013613 uses Sn (acetyl) 2 as

Catalyst and JP 05162237 teach the use of tin, zinc or cobalt carboxylates together with bonded ones

Hydrocarbon groups as silanol condensation catalysts, such as dioctyltin maleate, monobutyltin oxide, dimethyloxybutyltin or dibutyltin diacetate. JP 3656545 For crosslinking, zinc and aluminum soaps, such as zinc octylate, aluminum laurate, are used. JP 1042509 also discloses the use of silanes for crosslinking silanes

organic tin compounds, but also based on titanium chelate compounds Alkyltitansäureester.

The fatty acid reaction products of functional trichlorosilanes have generally been known since the 1960s,

especially as lubricant additives. DE 25 44 125 discloses the use of dimethyldicarboxylsilanes as a lubricant additive in the coating of magnetic tapes. In the absence of strong acids and bases, the compound is sufficiently stable to hydrolysis.

The object of the present invention is to provide novel carboxy-functionalized silicon-containing precursor compounds of organic acids which can be used as silane hydrolysis and / or silanol condensation catalysts which have the stated disadvantages of the known processes

Do not have catalysts of the prior art and preferably with silane-grafted, silane-co-polymerized polymers and / or monomers or prepolymers can be dispersed or homogenized and optionally polymerized. A special task was to specifically target the properties of the precursor compounds

in particular with regard to their solubility in organic media or their reactivity towards

Moisture or the reactivity towards polymerizable compounds or the spectrum of reactivity of the catalyst formed as well as the state of aggregation of the precursor ^¬ compound in order to simplify their handling. Another task was the reactivity of unsaturated hydrocarbon-containing carboxysilanes as a functional comonomer or silanizing agent

towards a polymerization reaction, for example, with respect to thermoplastic base polymers or also monomers, such as ethylene.

The problem is solved by the invention

A composition according to the features of claim 1, the formulation of the masterbatch according to claim 18 and the inventive methods having the features of claim 13 and by the use according to claim 17. Preferred

Embodiments are to be taken from the subclaims and preferably the description.

Surprisingly, it has been found that the composition comprising a hydrolyzable precursor compound of at least two different organic acids of the general formulas I and / or II, with respect to their property ^¬ spectrum by the correct choice of functionalized with different or different hydrocarbon radicals carboxy groups, preferably with R ³ is independently R ^3a , R ^3b and R ³ and optionally R ^3d , set to a given requirement profile of the subsequent application targeted.

Thus, by the right choice, for example, under ^¬ differently long fatty acids of the formula IV

comprising the fatty acids of the formulas IVa, IVb, IVc and

optionally IVd, in the preparation of the precursor compound to ensure that it is readily soluble in vinyltrimethoxysilane or vinyltriethoxysilane. Likewise, over the purposeful right choice of the different

Carboxylic acids of the formula IV in the preparation of Precursor compound of formula I and / or II the later

Release of the reactive catalysts, ie the acids of the formula IV and their reactivity in the polymerization process ^¬ controlled.

The invention provides a composition comprising at least one functionalized silicon containing precursor compound of organic acids, comprising at least one functionalized silicon-containing precursor ^¬ connection of two different organic acids, preferably from three or four different organic acids, particularly suitable as a silane hydrolysis catalyst and / or Silankondensationskatalysator or Catalyst precursor compound, and the carboxy-functionalized silicon

containing precursor compound has at least two, preferably three to four, functionalized with different hydrocarbon radicals carboxy groups and the general formula I and / or an oligomeric siloxane, in particular a dimer, trimer, low molecular weight oligomeric siloxane,

derived from the compound of general formula I according to the idealized general formula II

(A) _z SiR ² _x (OR ¹⁾ ₄ - _{(z +} x) (I) (R'O) [(R ¹ 0) ₂ - _(x + z) (R ²⁾ _x Si (A) _z O] _a [Si (A) _z (R ² ) _x (OR ¹ ) ₂ - (x + z) 0] _b R ¹ (II)

where in formulas I and II independently of one another z is 0, 1 or 2, x is 0, 1 or 2, with the proviso that (z + x) is less than or equal to (<) 2

- A independently of one another in formulas I and II

unsubstituted or substituted hydrocarbon group corresponds, in particular an unsubstituted or

 substituted linear, branched and / or cyclic alkyl, cycloalkenyl-alkylene, alkenyl, alkylaryl,

 Arylalkylene, aryl, preferably phenyl; Methacryloxyalkyl, acryloxyalkyl or halohydrocarbon group;

R ¹ independently corresponds in formula I and in formula II independently of one another at least two different carbonyl-R ³ groups, where R ^{3 is} selected from a substituted or unsubstituted hydrocarbon radical having 3 to 45 C atoms, preferably an unsubstituted hydrocarbon radical or with hydroxyl and / or carboxy groups substituted hydrocarbon radical, preferably R ¹ independently comprises R ^la = - (CO) R ^3a , R ^lb = - (CO) R ^3b and

R ^lc = - (CO) R ^3c and optionally R ^ld = - (CO) R ^3d ,

- R ² is independently in formula I and II are each independently an unsubstituted linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, in particular having 1 to 16 carbon atoms, preferably having 1 to 8 carbon atoms, especially preferably having 1 to 4 C atoms, or an aryl group, and

in formula II a are greater than or equal to (>) 1 and b are greater than or equal to (>) 1, in particular in Formula I and / or II x is 0 or 1, z is 0 or 1 and (x + z) is less than or equal to ( <) 2, preferably x + y is less than or equal to (<) 1, more preferably z = 0 or 1 and x = 0, as is preferably the case in olefinic carboxysilanes and / or tetracarboxysilanes of the formula I; or it comprises mixtures of these compounds. According to the invention the silicon-containing precursor ^¬ compound of formula I may be a carboxysilane, particularly an olefinic carboxysilane, in particular a silane tris- carboxy, and / or a Tetracarboxysilan, especially a tetra- -Carboxysilan be with various carboxy groups. The carboxysilane - the silicon-containing precursor compounds of various organic acids, in particular different fatty acids - can be present in the liquid phase and is thus easily metered. Alternatively, it may preferably be in the solid phase and thereby becomes inert to hydrolysis by atmospheric moisture. The olefinic

Carboxysilane of the formula I according to the invention is a so-called all-in-one package, because it can be co-polymerized or grafted and can simultaneously as adhesion promoter and / or

Silanhydrolysekatalysator and / or silanol condensation catalyst act. Preferably, the hydrolysis occurs

organic acid only with the supply of heat and moisture.

The carboxy-functionalized silicon is produced

containing precursor compound by reaction according to the

Reaction equations (a) or (b) of, for example but not exclusively, three or four organic acids of the general formula IV comprising the subgroups IVa, IVb, IVc and IVd. With formula IV equal to P ^ OH and the subgroup Iva = R ^la OH, IVb = R ^lb OH, IVc = R ^lc OH, IVd = R ^ld OH.

R ^la R OH + OH + R ^{lb lc ld} + R OH OH + SiCl ₄ -> ^■ Si (OR ^la) (OR ^{lb) (lc} OR) (OR ^ld) + 4 HCl (a)

R ^la R OH + OH + R ^{lb lc} OH + A-S1CI3 - "A-Si (OR ^{la) (lb} OR) (OR ^lc) + 3 HCl (b) R in formula I and / or II independently corresponds to different carbonyl-R ³ groups, ie different - (CO) R ³ groups (- (C = O) -R ³ ), so that each OR ^{1 is} preferably different -0 (CO) corresponds to R ³ , such as -O (CO) comprises R ³

-0 (CO) R ^3a, -0 (CO) R ^3b, -0 (CO) R ^3c, -0 (CO) R ^3d, wherein each R ³ (KW residue) corresponds to an unsubstituted or substituted hydrocarbon radical, in particular with 1 to 45 C atoms, preferably having 3 to 45 C atoms, in particular having 7 to 45 C atoms, more preferably 7 to 26 C atoms or 7 to 22, preferably having 8 to 45 C atoms, preferably having 8 to 22 C atoms, particularly preferably having 8 to 18 C atoms, preferably having 8 to 16 C atoms or else 8 to 13 or 14 C atoms,

in particular a linear, branched and / or cyclic unsubstituted and / or substituted hydrocarbon radical, more preferably a hydrocarbon radical of a natural or synthetic fatty acid, in particular each R ³ in R ^{1 is} independently a saturated hydrocarbon radical with -C _n H _{2 n} + i with n = 4 to 45, such as -C ₄ H ₉ , -C ₅ Hn, -C ₆ H ₁₃ , -C ₇ H ₁₅ ,

-C8H17, -C9H19, -C10H21, -C11H23 / ^_ Ci2H25 / ^_ Ci3H27 / ^_ Ci4H29 / -CisH3i,

-C ₁₆ H _33, -C ₁₇ H _35, -C ₁₈ H ₃₇ - C ₁₉ H _39, - C20H41, -C 2 H _{1 43 45} -C22H, -C 2 H _{3 47,} -C24H49, -C25H51, - C26H53, -C27H55, -C28H57 ,, -C29H59, or preferably also an unsaturated hydrocarbon radical, such as -C10H19,

-C H2 _{15 9 /} ^_ Ci ₇ H _33, -C ₁₇ H _33, -C ₁₉ H _37, - C21H41, -C2 ₁ H _41, - C21H41-C2 ₃ H _45,

-C ₁ 7H3 _1, -C ₁ 7H29 _/ ^_ Ci 7H29 _/ ^_ Ci9H3i, -C ₁ 9H29 _/ ^_ C2 iH33 and / or -C2 H3 _{1. 1} The shorter chain hydrocarbon radicals R ³ , such as -C ₄ H ₉ , -C ₃ H ₇ , -C ₂ H ₅ , -CH ₃ (acetyl) and / or R ³ = H (formyl) can also be used in the composition , Therefore, the general formula IV with R ¹ OH comprises the various acids of the subgrouping IVa R ^1a OH = HO (CO) R ^3a , IVb R ^1b OH = = HO (CO) R ^3b , IVc R ^lc OH = = HO (CO) R ^3c , IVd R ^ld OH = = HO (CO) R ^3d . Due to the low hydrophobicity of the hydrocarbon radicals, however, the composition is generally based on compounds of the

Formula I and / or II in which different R ¹ each have a carbonyl-R ³ group selected from the group R ³ , with an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms, having 7 to 45 carbon atoms, in particular with 7 to 26 C atoms, preferably with 7 to 22 C atoms, particularly preferably with 7 to 14 C atoms or

preferably with 7 to 13 carbon atoms.

As carbonyl-R ³ groups, comprising independently carbonyl-R ^{3a bls d} , the acid ^{radicals of} the organic carboxylic acids are understood, such as R ³ - (CO) -, as different carboxyl groups corresponding to the formulas I and / or II to the silicon according to Si -OR ¹ , as stated above, are bound. Generally, they can be functionalized with various hydrocarbon radicals

Carboxy groups (-OR ¹ with R ¹ = - (CO) -R ³ ), ie the acid residues of formula I and / or II are obtained from naturally occurring or synthetic fatty acids, such as the saturated fatty acids valeric acid (pentanoic acid, R ³ = C4H9), caproic acid

(Hexanoic acid, R ³ = C ₅ Hn), enanthic acid (heptanoic acid, R ³ = C 6H13), caprylic acid (octanoic acid, R ³ = C7H15), pelargonic acid (nonanoic acid R ³ = CsHi v), capric acid (decanoic acid, R ³ = C 9H19), lauric acid

(Dodecanoic ^R3 = C11H23), undecanoic acid (R ³ = C10H21),

Tridecanoic acid (R ³ = C12H25), myristic acid (tetradecanoic acid, ^R3 = C13H27), pentadecanoic, ^R3 = C14H29) palmitic acid

(Hexadecanoic, ^R3 = C15H31), margaric (heptadecanoic acid, ^R3 = C16H33), stearic acid (octadecanoic acid, R ³ = C17H35),

Nonadecandecanoic acid, (R ³ = C18H37), arachidic acid (eicosan / icosanoic acid, R ³ = C19H39), behenic acid (docosanoic acid, R ³ =

C21H43), lignoceric (tetracosanoic, ^R3 = C23H47),

Cerotic acid (hexacosanoic acid, R ³ = C25H51), montanic acid (Octaacosansäure, R = C ₂₇ H ₅₅ ) and / or melic acid (Triacontansäure, R ³ = C ₂₉ H ₅₉ ) but also the short-chain unsaturated fatty acids such as valeric acid (pentanoic acid, R ³ = C ₄ H ₉ ), butyric acid (butanoic acid, R ³ = C ₃ H ₇ ), propionic acid

(Propanoic acid, R ³ = C ₂ H ₅ ), acetic acid (R ³ = CH ₃ ) and / or

Formic acid (R ³ = H) and can be used as a silicon-containing precursor compound of the formula I and / or II, in particular as otherwise purely organic Silanolhydrolyse- and / or - condensation catalysts.

The invention also relates to compositions comprising compounds of the formula I and / or II obtainable from the

Reacting a compound of the formula III with two, three or four different fatty acids, in particular of the formulas IVa, IVb, IVc and optionally IVd, selected from caprylic acid, oleic acid, lauric acid, capric acid, stearic acid,

Palmitic acid, behenic acid and / or myristic acid

Preparation of the compound of the formula I and / or II, where particularly preferred fatty acids are selected from

Caprylic acid, lauric acid, capric acid, behenic acid and / or myristic acid.

The corresponding carboxy-silane compounds having different carboxy groups are shown, for example, in crosslinking reactions of methoxysilane-grafted PE-HD polymers, see

Embodiments, on average a better crosslinking than the free acids. Overall, the solid show

Carboxysilanes, with carboxy radicals greater than 14 carbon atoms significantly better crosslinking than the liquid carboxysilanes with carboxy radicals smaller than 14 carbon atoms and crosslink much better than the carboxysilanes with 3 identical carboxy radicals. Without wishing to be bound by theory, it is believed that when three out of four of the carboxy groups in the carboxysilane are more as 14 C atoms, ie 15 C atoms and more, the carboxysilanes produced are solid even if one of these carboxy groups has 14 C atoms or less (below 13 C atoms). In addition, a higher compatibility with the non-polar polymer matrix is generated, which manifests itself in a better distribution and, consequently, a better activity of the catalyst.

According to particularly preferred embodiments of the invention, in each case in formula I and / or II A a linear,

branched or cyclic alkyl, alkenyl, aryl, alkylaryl, aryl-alkylene, cycloalkenyl-alkylene, haloalkyl and / or acryloxyalkyl-functional group, in particular a linear, branched and / or cyclic alkyl group or

Cycloalkenyl-alkylene group having 1 to 18 carbon atoms and / or in each case a linear, branched and / or cyclic

Arylalkylene, haloalkyl, alkenyl, alkynyl and / or

Acryloxyalkyl group having in each case 1 to 18 C atoms and / or an aryl group having 6, 12 or 14 C atoms and / or an isoalkyl group having 1 to 18 C atoms, a cycloalkyl group having 1 to 18 C atoms such as a cyclohexyl group, 3-methacryloxypropyl group, a 3-acryloxypropyl group, fluoroalkyl group, vinyl group, allyl group, particularly preferably A is an alkenyl group, more preferably a vinyl group , or an alkyl group, more preferably a propyl or a haloalkyl group, such as preferably a 3-chloropropyl group. Likewise, preferably A is a cycloalkenyl-alkylene group having 1 to 16 carbon atoms,

preferably cyclohexenyl-alkylene having 1 to 8 carbon atoms in the bivalent alkylene group, more preferably one

Cyclohexenyl ethylene, more preferably a 3-cyclohexenyl ethylene group or also a 2-cyclohexenyl ethylene or 1 Cyclohexenyl-ethylene group, corresponding cyclohexenyl propylene groups are also preferred as cyclohexadienyl-alkylene groups having 1 to 4 carbon atoms in the bivalent

Alkylene group.

Likewise, A is preferably independently in

Formula I and / or II is a monovalent olefin group, such as

especially

C ₆ H ₉ - (CH ₂ ) ₂ -, preferably 3-C ₆ H ₉ - (CH ₂ ) ₂ -, 2-C ₆ H ₉ - (CH ₂ ) ₂ -, 1-C ₆ H ₉ - (CH ₂ ) 2 ^_ , or too

C ₆ H ₈ - (CH ₂ ) ₂ -, in particular 1, 3-C ₆ H ₈ - (CH ₂ ) ₂ - or 2, 4-C ₆ H ₈ - (CH ₂ ) ₂ - or

- (R ⁹ ) 2 C = C (R ⁹ ) -M _k -, wherein R ^{9 are the} same or different and R ^{9 is} a hydrogen atom or a methyl group or a

Phenyl group, the group M is a group from the group - CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -0 (0) C (CH ₂ ) ₃ - or -C (0) 0 is - (CH ₂ ) ₃ -, k is 0 or 1, such as vinyl, allyl, 3-methacryloxypropyl and / or acryloxypropyl, η 3 -pentenyl, n-4-butenyl or

 - Isoprenyl, 3-pentenyl, hexenyl, -alkylene cyclohexenyl having 1 to 8 carbon atoms in the bivalent alkylene group, preferably 1 to 4 carbon atoms; Ethylene-cyclohexenyl, cyclohexenyl,

 Cyclohexadiene, ethylene-cyclohexadiene, terpenyl, squalanyl, squalenyl, polyterpenyl, betulaprenoxy, cis / trans-polyisoprenyl, or

R ⁸ -F _g - [C (R ⁸ ) = C (R ⁸ ) -C (R ⁸ ) = C (R ⁸ )] _r -F _g -, wherein R ^{8 are the} same or different

and R ^{6 is} a hydrogen atom or an alkyl group having 1 to 3 C atoms or an aryl group or an aralkyl group, preferably a methyl group or a phenyl group, groups F are identical or different and F is a group from the series -CH ₂ - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -O (O) C (CH ₂ ) ₃ - or -C (O) 0- (CH ₂ ) 3-, r is 1 to 100, especially 1 or 2, and g is 0 or 1.

Preferably, no more alcohol is released when

at least one silicon-containing precursor compound of various organic acids, preferably of the general formula I with z = 1 or 2 and / or with z = 0 and different OR ¹

comprising -OR ^la = -0 (CO) R ^3a ; -OR ^lb = -0 (CO) R ^3b ; -OR ^lc = -O (CO) R ^3c and / or -OR ^ld = -O (CO) R ^3d with unsaturated carboxylate radicals, in particular a tetracarboxysilane, grafted onto a base polymer or with a monomer and / or prepolymer of the base polymer is co-polymerized, given ^¬ if grafted in the presence of a radical generator, or with a corresponding carboxyl-substituted silane

Base polymer is mixed and optionally after the

Shaping, preferably with heat, as catalyst causes crosslinking in the presence of moisture.

In addition, grafting or co-polymerizing in

Presence of an organofunctional silane compound, such as an unsaturated alkoxysilane of the general formula V

(B) _b SiR ⁴ _c (OR ⁵ ) 3-d- _c ), as defined below.

In the formula I it is preferred that z = 1 and x = 0 or z = 0 and x = 1 for the tricarboxysilanes and / or for the tetracarboxysilanes z = 0 and x = 0. Likewise preferred are

corresponding oligomeric siloxanes of the formula II.

Thus, based on various carboxylic acids or

various carboxylic acid-releasing silanes of the formula I and / or II are preferred, the two, three or four different carboxylic acids selected from capric acid, myristic acid, Caprylic acid, oleic acid, stearic acid, palmitic acid and lauric acid.

Particularly preferred compositions comprising precursor ^¬ compounds of formula I and / or II or the precursor compound of formula I or II as such or its

Mixtures in which

(i) each independently in formula I and / or II z is 1 and x is 0 and A is a linear, branched or cyclic alkyl, alkenyl, haloalkyl, cycloalkenyl-alkylene, especially cyclohexenyl-alkylene or alkenyl - group having 1 to 8 carbon atoms and R ¹ independently of one another two or three different carbonyl-R ³ groups (-

(C = O) R ³ groups), preferably three different

Carbonyl-R ³ groups corresponds, ie - (C = 0) R ³ is the same -

(C = 0) R ^{3a bls c} , wherein independently R ^{3 is} selected from an unsubstituted hydrocarbon radical having 3 to 45 carbon atoms, preferably an alkyl or alkenyl radical, in particular having 7 to 45 carbon atoms, preferably 7 to 26 C atoms or

(ii) each independently of one another in formula I and / or II z is 0 and x is 0 and R ¹ independently of one another corresponds to two, three or four different carbonyl-R ³ groups (- (C = 0) R ³ groups) ie, - (C = O) R ³ is the same - (C = O) R ^{3a to d} , where R ^{3 is} selected from an unsubstituted one

Hydrocarbon radical having 3 to 45 carbon atoms, preferably an alkyl or alkenyl radical, in particular having 7 to 45 carbon atoms, more preferably having 7 to 26 carbon atoms.

Surprisingly, it has been found that the physical state of the composition or of the precursor compound of the formula I and / or II or mixtures thereof can be adjusted, if specifically each independently in formula I and / or II

- R ¹ independently of each other at least two different

Carbonyl-R ³ groups (- (C = 0) R ^{3a to c or d} groups), preferably three or four, wherein in the various

Carbonyl-R ³ groups

(A) independently of one another at least one first R ³ radical is selected from an unsubstituted hydrocarbon radical having 3 to 14 C atoms, in particular having 7 to 14 C atoms, preferably 8 to 14 C atoms, preferably having 9 to 13 or 9 to 14 C atoms, preferably of alkyl or alkenyl radicals, and

(b) independently at least one further R ³ radical is independently selected from an unsubstituted one

 Hydrocarbon radical having 15 to 45 C-atoms, in particular 15 to 26 C-atoms, preferably 15 to 20 C-atoms, preferably of alkyl or alkenyl radicals.

Preferred abovementioned hydrocarbon radicals R ^{3 of} the carbonyl R ³ groups (- (C = O) R ³ groups) correspond to alkyl or alkenyl radicals having the stated number of C atoms.

The carboxy-functionalized silicon-containing precursor compounds of the formula I and / or II are preferably based on various fatty acid radicals, ie in particular on the reaction of a halosilane of the formula III with various fatty acids (R 1 H = R ^1a OH, R ^1b OH, R ^1c OH and or R ^ld OH), and each have a hydrophobic hydrocarbon radical which is sufficiently hydrophobic, has no unpleasant odor after release and does not bloom from the polymers produced. A KW residual is sufficiently hydrophobic if the respective Acid is dispersible in the polymer or a monomer or prepolymer. Particularly preferred acid radicals (-OR ¹ ) in the formulas I and / or II result from the following

Acids, such as capric, lauric, myristic,

Stearic acid, palmitic acid and / or behenic acid.

Likewise preferred are the different ones, of course

occurring or synthetic unsaturated fatty acids, ie at least one R ³ group in the different -OR ¹ in formula I and / or II corresponds with R ¹ = - (CO) -R ³ is R ^{la to d} = - (CO) -R ^{3a to d} , with R ^{3 of} an alkenyl group comprising

Cycloalkenyl-alkylene groups are converted to the precursor compounds of the formula I and / or II such that the compound of the formula I and / or II at least one of the following radicals R ³ in -OR ¹ = -0 (CO) -R ³ can have. These

Compounds of the formula I and / or II can be equal to two

On the one hand, they serve as silane hydrolysis catalysts and / or as silanol condensation catalysts or their precursors and can be replaced by their unsaturated counterparts

Hydrocarbon radicals (R ³ ) directly at the radical

Participate in polymerization. Preferred unsaturated fatty acids are sorbic acid (R ³ = C ₅ H _7), undecylenic acid (R ³ = C10H19),

Palmitoleic acid (R ³ = C15H29), oleic acid (R ³ = C17H33),

Elaidic acid (R ³ = C17H33), vaccenic acid (R ³ = C19H37), icosenoic acid (R ³ = C21H41), cetoleic acid (R ³ = C21H41), Erucansäure (R ³ =

C21H41), nervonic acid (R ³ = C23H45), linoleic acid (R ³ = C17H31),

alpha-linolenic acid ^(R3 = C17H29), gamma-linolenic acid (R ³ =

C17H29), arachidonic acid ^(R3 = C19H31), timnodonic (R ³ = C19H29), clupanodonic acid (R ³ = C21H33), ricinoleic acid (12-hydroxy-9-octadecenoic acid, (R ³ = C17H33O) and / or cervonic acid ⁽³ R = C21H31). Particular preference is given to precursor compounds of the formula I. and / or II containing at least one radical of oleic acid (R ³ = C ₁₇ H ₃₃ ).

Particularly preferred compositions comprise, in particular in addition to the abovementioned features, at least one carboxy-functionalized silicon-containing compound

Precursor compound of the formula I.

(iii) where z is 1 and A is H ₃ C (CH ₂ ) ₂ -, H ₂ C = CH ₂ -,

C1CH ₂ (CH ₂ ) ₂ -, cyclohexenyl-alkylene and / or

 Cyclohexadienyl-alkylene having 1 to 8 carbon atoms in the

bivalent alkylene group, such as C ₆ H ₉ - (CH ₂ ) ₂ -, preferably 3-C ₆ H ₉ - (CH ₂ ) ₂ -, 2-C ₆ H ₉ - (CH ₂ ) ₂ -, 1-C ₆ H ₉ - (CH ₂ ) ₂ -; or C ₆ H ₈ - (CH ₂ ) ₂ -, l, 3-C ₆ Hg- (CH ₂ ) ₂ - or 2, 4-C ₆ H ₈ - (CH ₂ ) ₂ - and OR ¹ in formula I. two or three different R ¹ (R ¹ = R ^{la bls c} ) selected from -COC ₇ H ₁₅ , -COC ₉ H ₁₉ , -COCnH ₂₃ , -COCi ₃ H ₂₇ , - COC15H31, -COC17H35 and -COC ₂ iH ₄₃ , or

(iv) with z equal to 0 and OR ¹ in formula I with two, three or four different R ¹ (R ¹ = R 1a ^{to d)} selected from -COC ₇ H ₁₅ , -COC ₉ H ₁₉ , -COCnH ₂₃ , - COCi ₃ H ₂₇ , -COC ₁ 5H _{3 1} , -COCi ₇ H ₃₅ and - COC ₂ iH ₄₃ ,

and optionally oligomeric compounds formed from the precursor compounds of the formula I according to the idealized formula II, in particular with a equal to 1 and b equal to 1, or a mixture of these.

Examples thereof are in particular with A equal to alkyl group, such as H ₃ C (CH ₂ ) ₂ -, (H ₉ C ₄ ) -, (H ₁₇ C ₈ ) -, (H ₃₃ Ci ₆ ) -; Alkenyl group, such as H ₂ C = CH ₂ -, cycloalkenyl-alkylene having 1 to 16 carbon atoms,

in particular cyclohexenylalkylene and / or cyclohexadienylalkylene having in each case 1 to 8 C atoms in the divalent alkylene group, in particular CeH ₉ - (CH ₂ ) ₂ -, 3-CeH ₉ - (CH ₂ ) ₂ - , 2-CeH ₉ - (CH ₂ ) ₂ -, 1-C ₆ H ₉ - (CH ₂ ) ₂ -, C ₆ H ₈ - (CH ₂ ) ₂ -, 1, 3-C ₆ H ₈ - (CH ₂ ) ₂ - or 2,4- C ₆ H ₈ - (CH ₂ ) ₂ -, in particular -ethylene-2-cyclohex-3-enyl or isomers with a different position of the double bond, and / or haloalkyl group, such as C ₁ CH ₂ (CH ₂ ) ₂ -:

A-Si (OCOC ₇ H ₁₅ ) _P (OCOCi iH ₂₃ ) p (OCOCi ₃ H ₂ 7) _P (myristyl, lauryl, capryl)

A -Si (OCOCi ₃ H ₂₇ ) _p (OCOCi ₅ H ₃ i) _P (OCOCi ₇ H ₃₅ ) p (myristyl, palmityl, stearyl)

(H ₁₉ C ₉ OCO) _p (A) Si (OCOC ₇ H ₁₅ ) _p (OCOCnH ₂₃ ) _p (OCOC ₁₃ H ₂₇ ) _p , (caprinyl, myristyl, lauryl, capryl);

(H ₄₃ C ₂₁ OCO) _p (A) Si (OCOC ₁₃ H ₂₇ ) _p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _P (behenyl,

Myristyl, palmityl, stearyl);

(H ₁₉ C ₉ OCO) _p (A) Si (OCOC ₇ H ₁₅ ) _p (OCOCnH ₂₃ ) _p (OCOC ₁₃ H ₂₇ ) _p ,

(H ₁₉ C ₉ OCO) _p Si (OCOC ₇ H ₁₅ ) _p (OCOCnH ₂₃ ) _p (OCOCi ₃ H ₂₇ ) _p , (caprinyl,

Myristyl, lauryl,

Capryl); (H ₄₃ C ₂₁ OCO) _p Si (OCOC ₁₃ H ₂₇ ) _p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _P with each p equal to 0, 1, 2 or 3, with the proviso that at least two different fatty acid residues p is 1 and the sum of all p per silicon compound is 3 is functionalized in Si-A substituted precursor compounds and the sum of all p equal to 4 in tetra-carboxy

Precursor compounds of the formula I, and optionally corresponding oligomeric compounds of the precursor compounds of the formula I according to the idealized formula II, in particular with a equal to 1 and b equal to 1, or a mixture of these.

Particularly preferred - but not limited itself - functionalized silicon-containing precursor ^¬ compounds of formula I are selected from

H ₃ C (CH ₂ ) ₂ -Si (OCOC ₇ H ₁₅ ) p (OCOCi iH ₂₃ ) p (OCOC ₁₃ H ₂₇ ) p,

H ₃ C (CH ₂ ) ₂ -Si (OCOC ₁₃ H ₂₇ ) _p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _P , H ₂ C = CH ₂ -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p,

H ₂ C = CH ₂ -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃ i) p (OCOC ₁₇ H ₃₅ ) _P.

C ₆ H ₉ - (CH ₂ ) ₂ -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) _p>

C ₆ H ₉ - (CH ₂ ) 2-Si (OCOC ₁₃ H ₂₇ ) _p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _p ,

C1CH ₂ (CH _{2) 2} Si (OCOC ₇ H _{15) p} (OCOCnH _{23) P} (OCOC ₁₃ H _{27) p,}

C1CH ₂ (CH _{2) 2} Si (OCOC ₁₃ H ₂₇₎ p (OCOC ₁₅ H _{31) p} (OCOC ₁₇ H _{35) P,}

(H ₁₉ C ₉ OCO) p (CICH ₂ (CH ₂ ) 2) Si (OCOC ₇ H ₁₅ ) p (OCOCnH ₂₃ ) _P (OCOC ₁₃ H ₂₇ ) _P ,

(H ₄₃ C ₂ iOCO) p (CICH ₂ (CH ₂ ) ₂ Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _p ,

(H ₁₉ C ₉ OCO) p (CICH ₂ (CH ₂ ) 2) Si (OCOC ₇ H ₁₅ ) p (OCOCnH ₂₃ ) _P (OCOC ₁₃ H ₂₇ ) _p ,

(H ₁₉ C ₉ OCO) _p Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p,

(H ₄₃ C ₂ iOCO) _p Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _P

(H ₃₃ C ₁₆ ) -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p

(H ₃₃ C ₁₆ ) -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P ,

(C ₁₇ H ₈₎ Si (OCOC ₇ H ₁₅₎ p (OCOC11H23) p (OCOC ₁₃ H ₂₇₎ p

(H ₁₇ C ₈ ) -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P ,

(H ₉ C ₄ ) -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p

(H ₉ C ₄ ) -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P , each with p equal to 0, 1, 2 or 3, with the proviso that at least two different carboxy groups p is 1, preferably at three different carboxy groups, and the sum of all p per silicon-containing precursor compound is 3, when in formula I z = 1 and the sum of all p is 4 in tetra-carboxy functionalized Precursor compounds of formula I with z = 0, and optionally corresponding oligomeric compounds of these

Precursor compounds or a mixture of these.

Further suitable acids from which the precursor compounds of the formula I and / or II with R ³ -COO or R ^x O can be prepared are glutaric acid, lactic acid (R ^{1 is the} same

(CH ₃ ) (HO) CH-), citric acid (R ¹ is HOOCCH ₂ C (COOH) (OH) CH ₂ -), Vulpinsäure, terephthalic acid, gluconic acid, adipic acid, wherein all carboxyl groups may be Si-functionalized, benzoic acid (R ¹ is phenyl), nicotinic acid (vitamin B3, B5). However, it is also possible to use the natural or also synthetic amino acids so that R ¹ corresponds to corresponding radicals, as starting from tryptohan, L-arginine, L-histidine, L-phenyalanine, L-leucine, preference being given to using L-leucine , Accordingly, the

corresponding D-amino acids or mixtures of L- and D-amino acids are used, or an acid, such as

D [(CH ₂ ) _d ) COOH] 3 with D = N, P and d independently = 1 to 12, preferably 1, 2, 3, 4, 5 or 6, in which independently the hydroxy group of each carboxylic acid function is Si functionalized can.

Thus, corresponding compounds of formula I and / or II based on radicals of these acids as

Silane hydrolysis and / or Silanolkondensations- be used.

The silicon-containing precursor compound of an organic acid is particularly in hydrolyzed form as

Silanhydrolyse- and / or -Silanolkondensationskatalysator on the released organic acid active and even in hydrolyzed or unhydrolyzed form for grafting on a polymer and / or co-polymerization with a

Base polymer, polymer / monomer or prepolymer or to

Crosslinking, for example as a primer suitable. In hydrolyzed form, the silanol compound formed in the condensation contributes to the crosslinking by means of formed Si-O-Si siloxane bridges and / or Si-O substrate or Si-O support material. This crosslinking can be done with other silanols, siloxanes or generally with functional groups suitable for crosslinking on substrates, fillers and / or carrier materials. Preferred fillers and / or carrier materials are therefore aluminum hydroxides, magnesium hydroxides, pyrogens

Silica, precipitated silica, silicates and other of the following fillers and support materials.

The alkyl group R ² is in particular linear,

branched or cyclic alkyl groups having 1 to 24 carbon atoms, preferably having 1 to 18 carbon atoms, particularly preferably having 1 to 4 carbon atoms in the case of alkyl groups. Particularly suitable alkyl groups R ² are ethyl, n-propyl and / or i-propyl groups. Suitable substituted alkyl groups are

in particular halogenated hydrocarbons, such as 3-halopropyl, for example 3-chloropropyl or 3-bromopropyl groups, which are optionally accessible to a nucleophilic substitution or which can be used in PVC. As the aryl group is phenyl or

Benzyl.

Thus, silicon-containing precursor compounds of an organic acid of general formula I and / or II are also preferred, the alkyl-substituted di- or tricarboxysilanes with z = 0 and x = 1 or 2 and based on various carboxylic acids or releases a silanol and various carboxylic acids. Examples thereof are methyl, dimethyl, ethyl or methylethyl-substituted carboxysilanes of the formula I, preferably based on two or three different

Carboxylic acids selected from capric acid, myristic acid,

Caprylic acid, oleic acid, stearic acid, palmitic acid and

Lauric acid. In order to facilitate ease of handling in the dosing of the composition comprising substantially carboxy-functionalized silicon-containing precursor compounds of formula I and / or II, according to an alternative, liquid precursor compounds may be preferred, especially those ranging from about 10 ° C to 80 ° C are liquid, in particular between 10 to 60 ° C, preferably between 10 to 40 ° C, more preferably between 10 to 35 ° C, each at atmospheric pressure (around 1013 hPa).

According to another preferred alternative, the

A composition comprising at least one precursor compound of the formula I and / or II applied to a carrier material, incorporated into a carrier material and / or encapsulated, in particular the carrier material is a mineral material or a thermoplastic base polymer, a silane-grafted base polymer, a silane-copolymerized base polymer Monomer of this base polymer, a prepolymer of this

Base polymers and / or mixtures of these. As mineral materials, such as fillers come

in particular also the following:

Preferred support materials and / or fillers are

Accordingly, metal hydroxides with stoichiometric proportion or, in their different dewatering stages, with substoichiometric proportion of hydroxyl groups to oxides with comparatively few remaining, but detectable by DRIFT-IR spectroscopy hydroxyl groups.

Examples of suitable carrier materials or fillers are aluminum trihydroxide (ATH), aluminum oxide hydroxide (AlOOH.aq), magnesium dihydroxide (MDH), brucite, huntite, hydromagnesite, mica and montmorillonite. Furthermore, as a filler Calcium carbonate, talc and glass fibers are used. Furthermore, so-called "char shapers", such as

Ammonium polyphosphate, stannates, borates, talc, or those used in combination with other fillers.

In addition, the composition may have further additives, such as titanium dioxide (Ti0 ₂ ), talc, clay, quartz, kaolin, bentonite, calcium carbonate (chalk, dolomite), or paints, pigments, talc, carbon black, S1O ₂ , precipitated silica, pyrogenic Silica, aluminas, such as alpha and / or gamma-alumina, alumina hydroxides, boehmite, barite, barium sulfate, lime, silicates, aluminates, aluminum silicates and / or ZnO or mixtures thereof. The carrier materials or additives, such as pigments, fillers, powdered, particulate, porous, swellable or possibly foamy, are preferably present.

Furthermore, a good dispersibility or homogenizability up to a good solubility of the composition comprising the carboxy-functionalized precursor compound of the formula I and / or II is desired, in particular in organofunctional silanes, organofunctional siloxanes, preferably also in silane-grafted, silane-co-polymerized Polymers, corresponding monomers or prepolymers. Especially

Thus, preferred are compositions comprising the

functionalized silicon-containing precursor ^¬ compound of Formula I, Formula II, or mixtures thereof having a solubility of greater than 40% in a hydrocarbon functionalized alkoxysilane or siloxane appropriate, in particular an alkenyl functionalized alkoxy silane or siloxane, preferably in vinyltrimethoxysilane, or Vinyltriethoxysilane, in particular, the solubility is greater than 50% in hydrocarbon-functionalized alkoxysilane.

Compositions according to the invention are particularly suitable for use in a monosil process, Sioplas processes with thermoplastic base polymers or a copolymerization process with monomers and / or prepolymers of thermoplastic base polymers.

In particular, the composition is essentially

anhydrous to prevent unwanted hydrolysis and / or

Prevent condensation prior to actual use in monosil, Sioplas or co-condensation processes.

The invention also relates to compositions,

in particular for the crosslinking of thermoplastic

Base polymers, preferably as a formulation comprising

at least one silicon-containing precursor compound of various organic acids of general formula I and / or II as defined above

Component-A, and

 optionally as component B, a radical generator and

optionally, as component C, an organofunctional silane compound,

 in particular an unsaturated alkoxysilane, preferably of the formula V,

(B) _b SiR ⁴ c (OR ⁵ ) 3-dc (V), wherein d, c, b, a, B, R ⁴ and R ⁵ are defined below, more preferably B is a vinyl group, especially unsaturated alkoxysilane, a vinyltriethoxysilane, vinyltrimethoxysilane or a mixture of these, optionally the composition is liquid, for example as silicon

 containing precursor compound of formula I and / or II, optionally together

 with an radical image, such as preferably dicumyl peroxide, tert. Butylcumyl peroxide, bis (tert-butylperoxy) diisopropylbenzene, 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane or 2, 5-dimethyl-2, 5-di-tert. -butylperoxy-hexane, in an unsaturated alkoxysilane, such as vinyltrimethoxysilane or vinyltriethoxysilane, in particular, it is dissolved in

 Alkoxysilane,

if appropriate, at least one of the preceding

Component A, B and / or -C be supported or encapsulated. In addition, the composition may also further formulation auxiliaries and / or processing aids as

Component (s) -D contain, such as stabilizers or other customary formulation auxiliaries.

Particularly preferred compositions, especially in the form of a formulation, comprise at least one silicon

containing precursor compound of various organic acids of general formula I and / or II or mixtures thereof as defined above as component A with 1 to 25 wt .-%, in particular 1.5 to 20 wt .-%, particularly preferably 2.0 to 18 , 0 wt .-%, and all intervening values, optionally as component B a free radical generator with 1 to 12 wt .-%, in particular 1.5 to 11 wt .-%, preferably 2 to 10 wt .-% and especially preferably 2.2 to 9.0 wt .-% and all intermediate values, and optionally as component-C is an organofunctional silane compound,

in particular an unsaturated alkoxysilane, preferably of the formula V, particularly preferably a vinyltrialkoxysilane, having 48 to 98 wt .-%, in particular 55 to 97.5 wt .-%, preferably 60 to 95, particularly preferably 70 to 92 wt .-%, particularly preferably 72 to 90 wt .-% and all intermediate values, and optionally as component (s) -D with 0 to 15.0 wt .-%, in particular 0.1 to 8.0 wt .-%, preferably 0.2 to 5.0 wt .-%, particularly preferably 0.5 to 3.0 wt .-% and all intermediate values, wherein in the aforementioned

Components independently in the composition give a total of 100 wt .-%.

A preferred composition, preferably as

Formulation, especially for the production of

Polymer compounds is suitable, contains as component-B at least one radical generator. Preferred free-radical initiators are organic peroxides and / or organic peresters or mixtures thereof, such as preferably tert. Butyl peroxypivalate, tert. Butyl peroxy-2-ethylhexanoate, dicumyl peroxide, di-tert. - Butyl peroxide, tert. Butyl cumyl peroxide, 1,3-di (2-tert-butylperoxy-isoproyl) benzene, 2, 5-dimethyl-2,5-bis (tert-butylperoxy) hexine (3), di-tert. -amyl peroxide, 1, 3, 5-tris (2-tert-butylperoxy-isopropyl) benzene, 1-phenyl-1-tert. - butyl peroxyphthalide, alpha, alpha '- bis (tert -butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di-tert. butylperoxyhexane, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane (TMCH). It is also expedient to use n-butyl-4,4-di (tert-butyl peroxy) valerate, ethyl 3,3-di (tert-butylperoxy) butoxide and / or 3, 3, 6, 9, 9 Hexamethyl-l, 2, 4, 5-tetraoxa-cyclononane be.

Likewise subject of the invention is a formulation comprising the composition of the invention or a A compound of the formula I, II or mixtures thereof, according to any one of claims 1 to 11.

Surprisingly, it has been found that the composition comprises the one hydrolyzable precursor compound of at least two different organic acids of the general formulas I and / or II and, if appropriate, additionally a

organofunctional silane compound, in particular of the formula V, as defined below, contains itself in a simple and economical manner with thermoplastic base polymers, monomers and / or prepolymers of the base polymers

Polymer compounds implement and the disadvantages mentioned, such as toxicity and odor impairment does not have. Depending on the composition, no more alcohols are released in the process for producing polymer compounds.

For example, if at least one silicon-containing precursor compound of various organic acids,

for example, the general formula I with z = 0, 1 or 2 and / or II, in particular z = 0 or 1, and OR ¹ corresponds to an unsaturated carboxylate radical, grafted onto a base polymer or with a monomer and / or prepolymer of Base polymer is co-polymerized, optionally in the presence of a radical generator, or with a corresponding carboxy-substituted silane-grafted base polymer

is mixed and optionally after the formation of a crosslinking in the presence of moisture.

Additionally or alternatively, the grafting or co-polymerizing in the presence of an organofunctional silane Compound, such as an unsaturated alkoxysilane of the general formula V, as defined below, take place.

Most preferably, the inventive

Composition as an organofunctional silane compound, in particular of the formula V, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldialkoxysilane, vinyltriethoxymethoxysilane (VTMOEO), vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane (MEMO ) and / or vinylethoxydimethoxysilane and / or allylalkoxysilanes, such as allyltriethoxysilane, unsaturated siloxanes, such as preferably oligomers

Vinylsiloxanes or mixtures of the compounds mentioned.

Preferred organofunctional silane compounds contain either a vinyl or methacrylic group, as these

Compounds reactive towards radicals and suitable for grafting onto a polymer chain or for co-polymerization with monomers, prepolymers.

The invention also provides a composition, in particular having the one or more of the aforementioned features, comprising a carboxy-functionalized silicon-containing precursor compound which has at least two functionalized with different hydrocarbon radicals

Having carboxy groups, preferably three or four

various carboxy groups, and is obtained from the

Reaction of a halosilane of the general formula III,

(A) _z Siir x (Hal) ₄ - (z + x) (HI) with z being 0, 1 or 2 and x being 0, 1 or 2 with (less than or equal to 2, A as defined above and below as defined, and Hai independently being chlorine or bromine having an at least molar stoichiometric ratio with respect to Halogen groups of the formula III with at least two different organic acids of the formula IV, ie of the formulas IVa and IVb according to subgrouping, or preferred

- at z equal to 1 and x equal 0 with an at least molar stoichiometric

Ratio with respect to the halogen groups of formula III with at least two or three different organic acids of formula IV, i. of formulas IVa, IVb and / or IVc, or preferably at z is 0 and x is 0 with an at least molar stoichiometric

Ratio with respect to the halogen groups of the formula III with at least two, three or four different organic

Acids of formula IV, i. Formulas IVa, IVb, IVc and / or IVd, wherein in the various organic acids of formula IV

LORD ¹ (IV)

R ¹ (ie R ^{1 a} _' ^lb ' ⁱ c and ^{d d i} _{d) independently of} one another in

Formula IV corresponds to different carbonyl-R ³ groups, ie carbonyl-R ^3a ' ^3b ' ^{3c and / or 3d} , wherein R ^{3 is} independently selected from a substituted or unsubstituted hydrocarbon radical having 3 to 45 C atoms, in particular having 7 to 45 C atoms, preferably 7 to 26 C atoms, particularly preferably 7 to 21 C atoms, or better 8 to 18 C atoms.

Preferably, the various organic acids of formula IV are used approximately equimolar, wherein the reaction is optionally carried out in the presence of an inert solvent, which is substantially removed after the reaction. The various acids of the formula IV can be used equimolar to one another, ie about 1: 1 for two different or different acids of the formula IV, or in the

Ratio of 50: 1 to 1: 50 respectively for the different acids used, regardless of whether two, three, four, five or six or even more different acids of formula IV are used. Preference is given to the various

Acids used approximately equimolar to each other, so in three different acids of formula IV about 1: 1: 1, in four different acids of formula IV about 1: 1: 1: 1. In general, the person skilled in the art knows that the molar ratios of the various organic acids can be chosen freely among one another, with a total of one carboxy-functionalized silicon

containing precursor compound with at least two with

different hydrocarbon radicals functionalized carboxy groups of formula I or II is obtained.

If it is preferred to prepare a compound of the formula II, the reaction is carried out at relatively high temperatures and with the addition of traces of water

extended. Preferably, the reaction is carried out in an inert solvent, in particular an organic inert solvent in which the compounds of formula III, IV, I and / or II are soluble, preferably only the reactants III and IV are soluble therein. Preferred solvents are hydrocarbons,

Halogenated hydrocarbons or ethers are preferred

aromatic hydrocarbons, such as toluene used.

In general, the skilled worker is also familiar with other customary inert, in particular hydrocarbon-based, solvents. Their suitability also depends on whether they are in one

Temperature range can be separated from the products, which leads to no significant reaction with the starting materials or to any significant decomposition of the products of formula I or II.

The invention also provides a process, in particular for preparing a carboxy-functionalized silicon-containing precursor compound of the formula I and / or II, preferably for preparing a composition comprising at least one carboxy-functionalized silicon-containing precursor compound of an organic acid having at least two, preferably three or four, with different

Hydrocarbon radicals functionalized carboxy groups, in particular of the formula I and / or II, by reacting a halosilane of the formula III

(A) _z SiR ² x (Hal) ₄ - (z + x) (HD

- where z is 0, 1 or 2, x is 0, 1 or 2 and (z + x) is less than or equal to (<) 2, - A is independently an unsubstituted or substituted

 Hydrocarbon group, in particular one

 unsubstituted or substituted linear, branched and / or cyclic alkyl, alkenyl, cycloalkenyl-alkylene having 1 to 8 C atoms in the bivalent alkylene group,

 Alkylaryl, arylalkylene, aryl, such as phenyl;

 Methacryloxyalkyl and / or acryloxyalkylyl group,

R ^{2 are} independently an unsubstituted linear, branched or cyclic

 Alkyl group having 1 to 24 carbon atoms or aryl group and

 Each Hai independently selected from a halogen group

Chlorine or bromine are, with at least two different organic acids

Formula IV, i. various formulas IV comprising IVa, IVb, IVc and / or IVd is implemented,

 - wherein in the different organic acids of formula IV

HÖR (IV)

- R (R = R ^la ' ^lb ' ^{lc and / o of ld} ) independently of one another

Carbonyl-R ³ group corresponds to (R ³ = R ^3a ' ^3b ' ^{3c and / or 3d} ), wherein R ^{: is} independently selected from a substituted or unsubstituted hydrocarbon radical having 3 to 45 carbon atoms, in particular having 7 to 45 carbon atoms , preferably 7 to 26 C atoms,

and the organic acids optionally at least in

molar stoichiometric ratio to the halogen groups of the formula III, optionally in the presence of an inert solvent. Particularly preferred are the aforementioned organic

Carboxylic acids, especially the naturally occurring or synthetic fatty acids, in particular the saturated

and / or unsaturated fatty acids used as organic acids of the formula IV in the process according to the invention.

In particular, this may be a selection of capric acid,

Caprylic acid, stearic acid, palmitic acid, oleic acid,

Lauric acid, myristic and behenic acid.

Particularly preferred in the process according to the invention are the various organic acids of formula IV

are used with each other in the ratio of 10: 1 to 1: 10, preferably the different acids of the formula IV

used with each other approximately equimolar and in particular the different acids of formula IV are at least approximately equimolar with respect to the halogen groups of the formula I.

used.

It is according to a preferred embodiment

preferred when a halosilane of the formula III with

 (v) z is 1 and x is 0 and A is an unsubstituted or substituted hydrocarbon group, in particular an alkyl, alkenyl, cyclohexenyl-alkylene having 1 to 8 C atoms in the bivalent alkylene group, alkylaryl, Arylalkylene, aryl, such as phenyl;

 Methacryloxyalkyl and / or acryloxyalkylyl group,

with two or three different organic acids of formula IV at least in the molar stoichiometric ratio with respect to the halogen groups of formula III or, with

(vi) z is 0 and x is 0 be reacted with two, three or four different organic acids of formula IV at least in the molar stoichiometric ratio with respect to the halogen groups of the formula III,

 - wherein in the different organic acids of formula IV

LORD ¹ (IV)

R ¹ independently of one another corresponds to a carbonyl-R ³ group, R ^{3 being} independently selected from a substituted or unsubstituted hydrocarbon radical having 3 to 45 C atoms, in particular having 7 to 45 C atoms, preferably 7 to 26 C atoms, more preferably 8 to 18 C-atoms, in particular 8 to 16 C-atoms.

Preferred examples of A groups are H 3 C (CH 2) 2, (H 9 C 4) -,

(H17C8) -, (H33C16) -, H2C = CH 2, CICH2 (CH ₂₎ 2 ~ r C6H9- _(CH2) 2 ~ r

in particular 3-C ₆ H ₉ - (CH ₂ ) ₂ -, 2-C ₆ H ₉ - (CH ₂ ) ₂ -, 1-C ₆ H ₉ - (CH ₂ ) ₂ -, C ₆ H ₈ - (CH ₂ ) ₂ -, 1, 3-C ₆ H ₈ - (CH ₂ ) ₂ - or 2,4-C ₆ H ₈ - (CH ₂ ) ₂ -, in particular cyclohex-3-enyl-2-ethylene and isomers such as cyclohex-2-enyl-2-ethylene or cyclohex-l-enyl-2-ethylene and mixtures of these or cyclohexadienyl-alkylene groups having 1 to 16 carbon atoms, in particular a cyclohexadienyl ethylene group.

Particularly preferred are two, three or four or more of the aforementioned saturated fatty acids and / or unsaturated fatty acids of general formula IV, in particular comprising IVa (R ^la OH), IVb (R ^lb OH), IVc (R ^lc OH) and / or IVd (R ^ld OH) reacted with a halosilane of the formula III. Preferably, three or four different fatty acids of the formula IV, in each case 1 mol, with 1 mol of trichlorosilane or 1 mol Tetrachlorosilane of the formula III, preferably in an inert solvent.

Preferred halosilanes are propyltrichlorosilane, cyclohex-3-enyl-2-ethylene-trichlorosilane, cyclohex-2-enyl-2-ethylene-trichlorosilane, cyclohex-1-enyl-2-ethylene-trichlorosilane, chloro-3-propyl-trichlorosilane , Vinyltrichlorosilane, allytrichlorosilane, tetrachlorosilane, n- / iso- / tert-butyltrichlorosilane, octyltrichlorosilane, n- / isohexadecyltrichlorosilane.

More preferably, the process is carried out in such a way that, in addition to or as an alternative to the abovementioned features, a compound of the general formula III

(v) where z is 1 and A is alkyl, such as H3C (CH2) 2 ^~, n- / iso- (H33C16) ^_,

(H ₁₇ C ₈ ) -, (H ₉ C ₄ ) -, alkenyl, such as H ₂ C = CH ₂ -, haloalkyl, such as CICH ₂ (CH ₂ ) 2, C ₆ H ₉ - (CH ₂ ) 2 -, in particular 3-C ₆ H ₉ - (CH _{2) 2} -, 2-C6H9- (CH ₂₎ 2 ^_, I-C6H9- (CH2) 2 ^_, CeHg - (CH ₂₎ 2 ^_, 1, 3 -CeHg - (CH 2) 2 ^_, or 2, 4-C6Hs- (CH2) 2 ^~, with shark equal to bromine or chlorine, preferably, Hal = Cl, with at least two or three different organic acids of the formula IV is reacted, in which R ^{Compound 1} , which comprises R ^{cis lc and / or ld} , is independently selected from -COC ₇ H ₁₅ , -COC ₉ H ₁₉ , -COC 11 H 23, -COCi ₃ H ₂₇ , -COC ₁₅ H 31, -COC 17 H 35 and -COC 21 H 43, or

 (vi) with z equal to 0

 with at least two, three or four different ones

organic acids of the formula IV is reacted, wherein R ¹ , comprising R ^{la to lc and / or ld} , is independently selected from - COC ₇ H ₁₅ , -COC ₉ H ₁₉ , -COC11H23, -COC13H27, -COC15H31, -COCi ₇ H ₃₅ and -C ₂₁ H ₄₃ .

The aforementioned reaction is preferably carried out with an at least equimolar Mixture of the different acids of the formula IV with respect to the halogen groups of the halosilane of the formula III used.

In general, the organic acids with longer hydrophobic hydrocarbon radicals, as mentioned above, beginning with the valeric acid, preferably capric acid, lauric acid and / or myristic acid, are well suited for the preparation of silanol condensation catalysts and as silanol condensation catalyst. The less hydrophobic acids, such as propionic acid, acetic acid, formic acid are to be classified as suitable for the reaction with thermoplastic hydrophobic polymers only. Accordingly, the odor-intensive fatty acids such as butyric acid and caprylic acid are due to the pungent odor only expedient or less suitable to be used in a composition, masterbatch or a method according to the invention. This applies in particular if the polymers to be produced or

Polymer compounds for the production of drinking water pipes

should continue to be used.

Organic acids are understood as meaning carboxylic acids which have no sulphate or sulphonic acid groups,

in particular, they are organic acids corresponding to R ³ -COOH.

Further suitable acids from which the precursor compounds of the formula I and / or II can be prepared with R ³ -COO- or P ² O- are described above, with glutaric acid, etc.

The silicon-containing precursor compound of various organic acids may be supported or filled be applied, which are described in detail above. Technically, this can be done by melting or dissolving in an inert solvent and adding the support materials or fillers or by the skilled person known per se.

In addition or as an alternative to the abovementioned process features, therefore, the composition produced of a silicon-containing precursor compound of an organic acid of the formula I and / or II can be applied to a carrier material, a filler, incorporated and / or encapsulated.

Another object of the invention is the use of a compound of formula I and / or II, a composition of a compound of formulas I and / or II or a mixture of these,

 in particular as catalyst precursor compound, preferably as silane hydrolysis catalyst and / or as silanol condensation catalyst,

 in the preparation of a silicon-containing polymer, polymer compound, an unfilled crosslinked polymer and / or a filled crosslinked polymer,

 in a monosil, Sioplas and / or co-polymerization process, in particular in a monosil process or Sioplas process with thermoplastic

Base polymers or in a co-polymerization process with monomers and / or prepolymers of thermoplastic

Base polymers in the presence of at least one free radical generator;

for the production of unfilled Si-crosslinked, and / or for the preparation of filled Si-crosslinked polymer compounds;

and / or appropriately filled Si-crosslinked or unfilled Si-crosslinked polymers based on thermoplastic

Base polymers, the filled polymers preferably comprise as fillers mineral particles and / or fibers, such as

Glass fibers, silicic acids, aluminum hydroxide, magnesium hydroxide and other fillers familiar to the expert.

Another object of the invention is also the use of a compound of formula I and / or II, a composition of a compound of formulas I and / or II or a mixture of these,

 in the presence of a thermoplastic base polymer, a silane-grafted base polymer, a silane-co-polymerized base polymer and / or in the presence of a monomer and / or prepolymer of these base polymers and / or mixtures thereof, or the use

 together with an organofunctional silane compound, in particular of the formula V as defined below, or

 together with other silanol condensation catalysts, in particular comprising dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin di (2-ethylhexanoate), dioctyltin di (isooctyl mercaptoacetate), dibutyltin dicarboxylate, monobutyltin tris (2-ethylhexanoate), dibutyltin dineodecanoate, laurylstannoxane, dibutyltin diketonoate, dioctyltin oxide,

Dibutyltin diacetate, dibutyltin maleate, dibutyltin dichloride, dibutyltin sulfide, dibutyltin oxide, organotin oxides, monobutyltin dihydroxy chloride, monobutyltin oxides, dibutyltin bis (isooctyl maleate), or

 in the manufacture of articles, in particular moldings, preferably of cables or pipes.

According to a particularly preferred embodiment, the use of a compound of formula I and / or II, a composition of a compound of formulas I and / or II or a mixture thereof, together with an organo-functional silane compound, in particular together with one having an unsaturated group

Alkoxysilane of the general formula V,

(B) _b SiR ⁴ _c (OR ⁵ ) ₃ -dc (V)

where, independently of one another, d is 0, 1, 2 or 3 and c is 0, 1, 2 or 3, with the proviso that in formula V c + d is less than or equal to (<) 3,

- with B independently of one another, a monovalent group in formula V, in particular an unsaturated hydrocarbon group, preferably (R ⁷ ) 2C = C (R ⁷ ) -E _q -, where R ^{7 are the} same or different and R ^{7 is a} hydrogen atom or a

Is methyl group or a phenyl group, the group E is a group from the series -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -0 (0) C (CH ₂ ) ₃ - or -C (0) 0- (CH ₂ ) ₃ -, q is 0 or 1, or isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl,

Squalenyl, polyterpenyl, betulaprenoxy, cis / trans-polyisoprenyl, or a group R ⁶ -D _p - [C (R ⁶ ) = C (R ⁶ ) -

C (R ⁶ ) = C (R ⁶ )] t - D _p - wherein R ^{6 are the} same or different and R ^{6 is} a hydrogen atom or an alkyl group having 1 to 3 C atoms or an aryl group or an aralkyl group, preferably one Methyl group or a phenyl group,

D represents a group from the series -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -0 (0) C (CH ₂ ) ₃ - or - C (O) 0- (CH ₂ ) 3- and p is 0 or 1 and t is 1 or 2, more preferably a vinyl group;

R ⁵ is independently methyl, ethyl, n-propyl and / or iso-propyl, R ⁴ is independently a substituted or unsubstituted hydrocarbon group, in particular an alkyl group having 1 to 16 carbon atoms or an aryl group.

The invention likewise relates to a formulation comprising the composition according to the invention, in particular a masterbatch containing a composition or a compound of the formula I or II according to any one of claims 1 to 16, in particular for crosslinking thermoplastic

Base polymer containing at least one silicon

A precursor compound of an organic acid of the formula I and / or of the formula II and a thermoplastic base polymer, a silane-grafted base polymer, a silane-co-polymerized base polymer, a monomer of these base polymers, a prepolymer of these base polymers and / or

Mixtures of these, and optionally comprises a radical generator.

As thermoplastic base polymers in the context of the invention, the following compounds are considered: a silane-grafted base polymer, a silane-co-polymerized

Base polymer and / or monomer and / or prepolymer thereof

Base polymers, or else silane block co-prepolymers or block co-prepolymers and / or mixtures thereof. Preferably, the thermoplastic base polymer is a nonpolar polyolefin, such as polyethylene, polypropylene or a polyvinyl chloride or a silane-grafted polyolefin and / or silane-co-polymerized polyolefin and / or a copolymer of one or more olefins and one or more co-monomers contain polar groups. The thermoplastic base polymer can also act partially or completely as a carrier material, for example in a masterbatch comprising as support material a thermoplastic base ^¬ polymer or a polymer and the silicon-containing

Precursor compound of an organic acid of formula I and / or II and optionally an organofunctional

Silane compound, in particular of the formula V.

Preferred thermoplastic base polymers of the invention are, in particular acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polymethyl methacrylate (PMMA), polycarbonate (PC),

Polyethylene (PE), polypropylene (PP), polystyrene (PS),

Polyvinyl chloride (PVC) as well as on ethylene units

based polymers ethylene-vinyl acetate copolymers (EVA), EPDM or EPM and / or celluloid or silane-co-polymerized polymers understood and as monomers and / or prepolymers precursors of these base polymers, such as ethylene, propylene. Other thermoplastic base polymers are

mentioned below.

Examples of silane-co-polymerized thermoplastic

Base polymers are also ethylene-silane copolymers,

For example, ethylene-vinyltrimethoxysilane co-polymer,

Ethylene-vinyltriethoxysilane co-polymer, ethylene-dimethoxyethoxysilane co-polymer, ethylene-gamma-trimethoxysilane copolymer, ethylene-gamma (meth) acryloxypropyltriethoxysilane copolymer, ethylene-gamma-acryloxypropyltriethoxysilane copolymer, ethylene-gamma (meth) acryloxypropyltrimethoxysilane copolymer, ethylene-gamma-acryloxypropyltrimethoxysilane copolymer and / or ethylene-triacetoxysilane co-polymer.

As a non-polar thermoplastic base polymers thermal ^¬ plaste as, in particular, a pure PE-type can be used, for example, PE-LD, PE-LLD, PE-HD, m-PE. Polar groups supporting base polymers give z. B. an improved

Fire behavior, d. H. lower flammability and

Flue gas density, and increase the Füllstoffaufnahmevermögen. Polar groups are z. As hydroxyl, nitrile, carbonyl, carboxyl, acyl, acyloxy, carboalkoxy or

Amino groups and halogen atoms, in particular chlorine atoms.

Non-polar are olefinic double bonds or C-C triple bonds. Suitable polymers are in addition to polyvinyl chloride co-polymers of one or more olefins and one or more co-monomers containing polar groups, for. As vinyl acetate, vinyl propionate, (meth) acrylic acid, (meth) - acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) - butyl acrylate, acrylonitrile. The copolymers contain the polar groups, for example in amounts of from 0.1 to 50 mol%, preferably from 5 to 30 mol%, based on the polyolefin units. Particularly suitable base polymers are ethylene-vinyl acetate copolymers (EVA). For example, a suitable commercial copolymer contains 19 mole% vinyl acetate and 81 mole% ethylene building blocks.

Particularly suitable base polymers are polyethylene,

Polypropylene, as well as correspondingly silane-modified polymers. The silane-grafted polymers may be filled or unfilled with fillers and optionally after one

Shaping, moisture crosslinking.

The composition or the masterbatch according to the invention are suitable as additive in a monosil, Sioplas and / or in a co-polymerization process or process. The silane hydrolysis and / or silanol condensation catalyst of the general formula I and / or II is particularly effective only when additional moisture is added. Therefore finds the final cross-linking of unfilled or filled

Polymers generally in a known manner in a water bath, in a steam bath, or by atmospheric humidity at ambient temperatures ^¬ temperature (so-called "ambient curing") instead.

The masterbatch may contain as a further component a stabilizer and / or further additives and / or mixtures thereof.

The invention also provides a silicon-containing precursor compound of the general formula I and / or II, in particular as defined in any one of claims 1 to 9 or 13 to 16.

The following examples illustrate the invention

Compositions, the masterbatch and the inventive method in more detail, without limiting the invention to these examples.

Determination methods:

 Hydrolyzable chloride (chloride) was titrated potentiographically with silver nitrate (for example Metrohm, type 682

Silver rod as indicator electrode and Ag / AgCl reference electrode or other suitable reference electrode).

Total chloride content after Wurtzschmitt digestion. For this purpose, the sample is digested in a Wurtzschmittbombe with sodium peroxide. After acidification with nitric acid, chloride is potentiographically measured with silver nitrate as above.

General production methods:

A) Preparation of functionalized with different hydrocarbon radicals carbonyl groups Carboxysilanes, such as haloalkyl, alkyl, Alkenyltricarboxyl- silane, which are hereinafter also referred to as A-tricarboxysilane or tetracarboxysilane.

General examples:

a) For the preparation of A-tricarboxysilanes (formula I with z = 1) 1 mol of an A-trichlorosilane, or generally an A-trihalosilane, with 3 mol or an excess of two or three different organic mono-carboxylic acid of the formula IV is selected from R ^la OH, R ^lb OH and R ^lc OH reacted directly or in an inert solvent, in particular at elevated

Temperature, implemented. Preferably, 1 mol of A-trichlorosilane with a mixture of 1 mol of a first organic mono-carboxylic acid (R ^la OH), 1 mol of a second organic mono-carboxylic acid (R ^lb OH) and 1 mol of a third organic mono-carboxylic acid (R ^lc OH) reacted. When reacted with only two different mono-carboxylic acids, they can be used in the ratio of 1: 2 to 2: 1, preferably 1: 1, ie in each case to 1.5 mol. The reaction preferably takes place at elevated temperature, for example up to the boiling point of the solvent or around the melting point of the organic fatty acid or of the organic acid. b) For the preparation of tetracarboxysilanes 1 mol

 Tetrahalosilane, especially tetrachlorosilane or

Tetrabromsilan, with 4 mol or an excess of two, in particular three or four different mono-carboxylic acids of formula IV selected from R ^la OH, R ^lb OH, R ^lc OH and R ^ld OH, for example, different fatty acids or one

 Fatty acid mixture of these fatty acids implemented. The reaction can be directly by melting or in an inert

Solvent, preferably at elevated temperature, take place. execution

 Preparation, characterization of the following carboxysilanes from TCS, VTC and STC with

 - 3 (or 4) different, long-chain carboxylic acids with regard to the state of matter (solid, wax, liquid)

Example 1: Preparation of vinylcarboxysilanes

 Example 1.1: Vinylcarboxysilane from lauric, myristic and

caprylic

 Table 1: Overview

Procedure: Synthesis with three different fatty acids (= <C14) with vinyltrichlorosilane (VTC); Test batch: 200g

(Chain length R ^{1 of} the fatty acids R ^{la c} = C8, C12, C14)

Table 2: starting materials Dimensions

 Product Molar mass Mol Mass (%)

 (should)

 Carboxysilane 624, 5 1 85, 1% 170.2

 HCl 36, 5 3 14, 9% 29, 8

 Table 3: Product (intended)

synthesis

 The fatty acids mentioned were mixed with 100 g of toluene in the

Submitted reaction flask, mixed and heated to about 60 ° C. By dropping funnel was added dropwise over 15 min ^¬ vinyl trichlorosilane. It is a slight increase in temperature to watch. After the addition, 15 min. stirred and then raised the temperature of the oil bath to 150 ° C. During the stirring, a gas evolution (HC1 gas) was observed. By means of a wash bottle, filled with NaOH + water, HCl was neutralized. It was 3.5 hours

stirred.

distillation

 The oil bath was heated to 80 ° C. It was on

Rotary evaporator at a pressure of <lmbar in one

Cold trap (dry ice and isopropanol, ca. -80 ° C) deducted. Subsequently, lh is stirred.

The product obtained is liquid, slightly viscous, slightly yellow. Toluene was mainly removed on a rotary evaporator.

Weight: Carboxysilane: 169.9 g (Yield 99.82%)

NMR analysis of the carboxysilane

The 1H and 13C NMR spectra show the reaction product of vinyltrichlorosilane with the various fatty acids. It contains proportions of excess free acid, (about 8 mol%). Si NMR spectrum

 about 4.7% Si in the silane range

 about 84.0% Si in the vinyltricarboxysilane range

 about 11.3% Si M structures derived from vinyltricarboxysilane

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 4: Chloride determination

Solubility study in solvent:

 Table 5: Solubility

 It became a liquid, slightly yellow and slightly viscous vinylcarboxysilane of the three different fatty acids

 produced .

Example 1.2: Vinylcarboxysilane from myristic, palmitic and stearic acid

Table 6: Overview Execution :

 Preparation of vinyltricarboxysilane with a mixture of three different fatty acids (> = C14) with vinyltrichlorosilane (VTC); Test batch: 200g

(Chain length R ^{1 of} the fatty acids R ^{la c} = C14, C16, C18)

 Table 7: Educts I

 Table 8: Product (should)

synthesis

 The three fatty acids were mixed with 100g of toluene in the

 Submitted reaction flask, mixed and heated to about 60 ° C. By means of a dropping funnel, vinyltrichlorosilane was added dropwise within 15 minutes. It was a slight increase in temperature too

observe. After the addition, stirring is continued for 15 minutes and then the temperature of the oil bath is raised to 150.degree. During the stirring, a gas evolution (HCl gas) was observed. By means of a wash bottle, filled with NaOH + water, HCl was neutralized. It was stirred for 3.5 hours. distillation

 At an oil bath temperature of 85 ° C., volatile constituents were removed on a rotary evaporator (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.). Subsequently, lh was stirred. A white solid product was obtained. In the cold trap, 97.5% of the toluene was collected.

 Weighing: Carboxysilane: 174.3g (Yield 99, 75%), NMR analysis of the Carboxysilane

The ¹ R and ¹³ C NMR spectra show the reaction product of vinyltrichlorosilane with the fatty acids. It contains proportions of excess free acid, (about 10 mol%).

²⁹ Si NMR spectrum

 about 2% Si in the silane range

 about 82.1% Si in the vinyltricarboxysilane range

 about 15.8% Si M structures derived from vinyltricarboxysilane

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 9: Chloride determination

Solubility study in solvent:

Table 10: Solubility It was a solid, white Vmylcarboxysilan made with the different fatty acids.

Example 2: Preparation of vinylcarboxysilanes with

 Propyltrichlorosilane (PTCS)

 Example 2.1: Preparation of Propyltricarboxysilane

 Table 11: Overview

Procedure: Synthesis with three different fatty acids (= <C14) with propyltrichlorosilane (PTCS); Test batch: 200g

(Chain length of different fatty acids

Table 12: Edukte Product Molar mass Mol Mass (%) Mass (should)

Propylcarboxysilane 641, 0 1 85.4% 170.8

 HCl 36, 5 3 14, 6% 29, 2

 Table 13: Product (should)

synthesis

 The fatty acids were introduced into the reaction flask with 100 g of toluene, mixed and heated to about 60 ° C. through

Dropping funnel was added dropwise within 15 min of propyltrichlorosilane (PTCS). It was not a temperature increase too

observe. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the

After stirring, a gas evolution (HCl gas) was observed. By means of a wash bottle, filled with NaOH + water, the HCl was neutralized. It was stirred for 3.5 hours.

distillation

 An oil bath of a rotary evaporator was heated to 85 ° C. (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.) and volatile constituents were stripped off.

Subsequently, lh was stirred. The toluene could be distilled off to 98.2%. A liquid, slightly viscous, slightly yellow product was obtained.

Weight: Carboxysilane: 167.7g (98.13%)

NMR analysis of the carboxysilane

The ¹ R and ¹³ C NMR spectra show the reaction product of propyltrichlorosilane with the fatty acids. In addition, about 5% of free acid is present. Si NMR spectrum

 about 90.0% Si in the tricarboxysilane range

 about 8.1% Si M structures

 approx. 1.9% Si additional signal at -24 ppm (silicone)

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 14: Chloride determination

Solubility study in different solvents

 Table 15: Solubility

It became a liquid, slightly yellow, slightly viscous

 Propylcarboxysilane made of the three different fatty acids.

Example 2.2: Propyltrichlorosilane with myristic, palmitic, and stearic acid

 Table 16: Overview

Procedure: Synthesis with different fatty acids (> = C14) with propyltrichlosilan (PTCS); Test batch: 200g

(Chain length of the fatty acids

 Table 17:

 Table 18: Product (should)

synthesis

The three fatty acids were initially charged with 100 g of toluene in the reaction flask ^¬, mixed and heated to about 60 ° C. By means of dropping funnel, propyltrichlorosilane (PTCS) was added dropwise within 15 minutes. It was not a temperature increase too

 observe. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the

After stirring, a gas evolution (HCl gas) was observed. By means of a wash bottle filled with NaOH + water and a slight vacuum, HCl was neutralized. It was stirred for 3.5 hours.

distillation

 The oil bath of a rotary evaporator was heated to 85 ° C. (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.) and the volatiles were removed. It was stirred after. The toluene became essentially

 distilled off. A white, solid product was obtained

 Weight: Carboxysilane: 174.0g (98.3%)

NMR analysis of the carboxysilane

The ¹ R and ¹³ C NMR spectra show the reaction product of propyltrichlorosilane with the three fatty acids. In addition, there are about 13% free acid.

²⁹ Si NMR spectrum

 about 74.6% Si in the range carboxysilane

 approx. 22.3% Si M structures (derived from the carboxysilanes) approx. 0.4% Si D structures (derived from the carboxysilanes) approx. 2.7% Si additional signal at -24 ppm (silicone)

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

Table 19: Chloride determination Solubility study in solvent

 Table 20: Solubility

A solid white propylcarboxysilane of the three different fatty acids was prepared.

Example 3: Reaction of tetrachlorosilane (SiCl ₄ ) with various fatty acids

 Example 3.1: Tetrachlorosilane with caprylic, capric, lauric and myristic acid

 Ta e e: U ss t

Procedure: Synthesis with four different fatty acids (= <C14) and tetrachlorosilane (S1CI ₄ ), test batch: 200g

(Chain length of fatty acids R ^ia - ^ca _: c8, C10 C12, C14)

Quantity of molar mass

 Educts m (actual) [g]

 [mol] [g / mol]

 caprylic

 31.5 1 144.2

 (liquid)

 Capric acid 37, 7 1 172.3

 Toluene 100.0 92, 14

 Table 22: Educts

 Table 23: Product (should)

synthesis

 The four fatty acids were mixed with 100g toluene in the

Submitted reaction flask, mixed and heated to ca.50 ° C. By means of dropping funnel tetrachlorosilane (S1CI ₄ ) was added dropwise within 15 min. It was not a temperature increase too

observe. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the stirring, a gas evolution (HCl gas) was observed. By means of a wash bottle, filled with NaOH + water, with slight negative pressure, HCl was neutralized. It was stirred for 3.5 hours.

distillation

 The oil bath of the rotary evaporator was heated to 85 ° C. (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.) and volatile constituents were stripped off.

Subsequently, lh was stirred. Toluene was in the Essentially completely distilled off. The product is liquid, slightly viscous, slightly yellow.

 Weight: Carboxysilane: 164.4g (97.80%)

NMR analysis of the carboxysilane

The ¹ R and ¹³ C NMR spectra show the reaction product of tetrachlorosilane with the four fatty acids. In addition, about 15% of free acid is present.

²⁹ Si NMR spectrum

 about 60.0% Si in the range tetracarboxysilane

 Approx. 35.5% Si M structures derived from tetracaboxysilane approx. 4.5% Si D structures derived from tetracaboxysilane

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 24: Chloride determination

Solubility study in solvent

 Table 25: Solubility

It became a liquid, slightly yellow, slightly viscous

 Silicon carboxysilane of the four different fatty acids

produced . Example 3.2: Tetrachlorosilane with myristic, palmitic, stearic and behenic acid

 Table 26: Overview

execution

Synthesis with four different fatty acids (> = C14) with tetrachlorosilane (S1CI ₄ ),

 Test batch: 200g

Chain length of the fatty acids R ^ia -: C14, C16, C18, C22)

 Table 27: Educts

Table 28: Product (should) synthesis

 The four fatty acids were mixed with 100g toluene in the

Submitted reaction flask, mixed and heated to ca.50 ° C. By means of dropping funnel tetrachlorosilane (S1CI ₄ ) was added dropwise within 15 min. It was not a temperature increase too

observe. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the stirring, gas evolution (HCl gas) was too

observe. By means of a wash bottle, filled with NaOH + water, with slight negative pressure, HCl was neutralized. It was stirred for 3.5 hours.

distillation

 The oil bath of the rotary evaporator was heated to 85 ° C. (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.) and volatile constituents were stripped off.

Subsequently, lh was stirred. Toluene was in the

Essentially completely removed. A white, solid product was obtained.

Weight: Carboxysilane: 174.1g (97.80%)

NMR analysis of the carboxysilane

The ¹ R and ¹³ C NMR spectra of the sample show tetracarboxysilane with the various fatty acid residues and additional

Proportions of free carboxylic acid (about 15%).

²⁹ Si NMR spectrum

 66.3% Si tetracarboxysilane

 28.3% Si M structures derived from tetracarboxysilane

5.4% Si D structures derived from tetracarboxysilane

Chloride determination: Chloride determination was also carried out on the produced carboxysilane. Determination result unit

 Total chloride <0.1% (mass)

 Table 29: Chloride determination

Solubility study in solvent

 Table 30: Solubility

A solid white silicon carboxy silane of the four different fatty acids was prepared.

Example 3.3: Tetrachlorosilane with caprylic, palmitic, stearic and behenic acid

 Ta e e: U ss t

execution

Synthesis with four different fatty acids with tetrachloride (SiCl ₄ ),

Test batch: 200g (Chain length of the fatty acids R ^{ia "ca} - _: c 8, C16, C18, C22)

 Table 32: Educts

 Table 33: Product (should)

synthesis

The four fatty acids were initially charged with 100 g of toluene in the reaction flask ^¬, mixed and heated to about 50 ° C. By means of dropping funnel tetrachlorosilane (SiCl ₄ ) was added dropwise within 15 min. There was no increase in temperature. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the stirring, a gas evolution (HCl gas) was observed. By means of a wash bottle, filled with NaOH + water, with slight negative pressure, HCl was neutralized. It was stirred for 3.5 hours. distillation

 The oil bath of the rotary evaporator was heated to 85 ° C. (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.) and volatile constituents were stripped off.

 Subsequently, lh was stirred. The toluene could in the

 Essentially completely removed. A solid, white product was obtained.

 Weight: Carboxysilane: 172.2g (98.06%) NMR analysis of the carboxy silane

The ¹ R and ¹³ C NMR spectra of the sample show tetracarboxysilane of the various fatty acids with additional levels of free carboxylic acid (about 20%).

²⁹ Si NMR spectrum

 60.5% Si tetracarboxysilane

 28.5% Si M structures derived from tetracarboxysilane

 11.0% Si D structures derived from tetracarboxysilane

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 34: Chloride determination

Solubility study in solvent

Table 35: Solubility It was synthesized from S1CI ₄ with three long-chain fatty acids and a short-chain fatty acid, a carboxysilane. However, the short-chain fatty acid had no effect on the consistency of the Siliciumcarboxysilanes. A solid, white product was obtained.

Example 4: Reaction of 3-chloropropyltrichlorosilane (CPTCS) with various fatty acids

The CPTCS was purified via a Vigreux.

Example 4.1: Implementation of CPTCS with caprylic, capric, lauric and myristic acids

 Table 36: Overview

Synthesis with four different fatty acids with 3-chloropropyltrichlorosilane (CPTCS)

 Test batch: 200g

(Chain length of fatty acids R ^ia - ^ca - _: c8, C10 C12, C14)

caprylic

 30.1 1 144.2

 (liquid)

 Capric acid 36, 0 1 172.3

 Toluene 100.0 92, 14

 Table 37: Educts

 Table 38: Product (should)

synthesis

 The four fatty acids were mixed with 100g toluene in the

Submitted reaction flask, mixed and heated to ca.50 ° C. By means of dropping funnel was within 15 min

Chloropropyltrichlorosilane (CPTCS) was added dropwise. There was no increase in temperature. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the stirring, a gas evolution (HC1 gas) was observed. By means of a wash bottle, filled with NaOH + water, with slight negative pressure, HCl was neutralized. It was stirred for 3.5 hours.

distillation

 The oil bath of the rotary evaporator was heated to 85 ° C. (pressure <1 mbar, cold trap, with dry ice and isopropanol to about -80 ° C.) and volatile constituents were stripped off.

Subsequently, lh was stirred. Toluene was in the

Essentially completely removed. A liquid, slightly viscous and slightly yellow product was obtained.

Weighing: Carboxysilane: 173.8g NMR analysis of the carboxysilane

The ¹ R and ¹³ C NMR spectra show the reaction product of chloropropyltrichlorosilane with the various fatty acids. The chlorine atoms on the silicon were exchanged while the

 Chloropropyl remains unchanged. Accordingly, portions of excess free acid are present.

²⁹ Si NMR spectrum

 about 82.8% Si in the range silane (Chlorpropyltricarboxysilan) about 17.2% Si M structures

Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 39: Chloride determination

Solubility study in solvent

 Table 40: Solubility

A liquid, slightly viscous propylcarboxysilane of the three different fatty acids was prepared. Example 4.2: CPTCS with myristic, palmitic, stearic and behenic acid

 Table 41: Overview

Synthesis with four different fatty acids with 3-chloropropyltrichlorosilane (CPTCS),

 Test batch: 200g

(Chain length of the fatty acids R ^{ia "ca} - _: ci4, C16, C18, C22)

 Table 42: educts

Table 43: Product (should) synthesis

The four fatty acids were initially charged with 100 g of toluene in the reaction flask ^¬, mixed and heated to about 50 ° C. By means of a dropping funnel, 3-chloropropyltrichlorosilane (CPTCS) was added dropwise within 15 minutes. There was no increase in temperature. After the addition, stirring was continued for 15 minutes, after which the temperature of the oil bath was raised to 150.degree. During the stirring, a gas evolution (HCl gas) was observed. By means of a wash bottle, filled with NaOH + water, with slight negative pressure, HCl was neutralized. It was stirred for 3.5 hours.

distillation

 The oil bath was heated to 85 ° C, by means of rotary evaporator (pressure to <lmbar, cold trap, with dry ice and isopropanol to about -80 ° C) volatiles were removed. It was stirred after. Toluene could be almost completely removed. The product obtained is solid and white.

Weighing: Carboxysilane: 181.2g

 NMR analysis of the carboxysilane (Test Report No. A090023426

The ¹ R and ¹³ C NMR spectra show the reaction product of chloropropyltrichlorosilane with fatty acids. The chlorine atoms on the silicon have been exchanged, while the chloropropyl remains unchanged. Accordingly, there are shares

excess free acid.

²⁹ Si NMR spectrum

 74.5% Si silane (Carboxysilane)

 24.2% Si M structures (derived from carboxysilane)

1.3% Si D structures (derived from carboxysilane) Chloride determination: Chloride determination was also carried out on the produced carboxysilane.

 Table 44: Chloride determination

Solubility study in solvent

 Table 45: Solubility

A solid, white propylcarboxysilane of the three different fatty acids was prepared.

Summary of the Results of Examples 1 to 4:

Table 46: Carboxysilanes containing three to four different carboxy radicals were successfully prepared. In the crude carboxysilane are 5 - 20% free fatty acid, which may result from the formation of dimers and trimers. In CPTCS, however, the chlorine of the propyl group could not be substituted.

SiCl ₄ was synthesized with 3 long-chain fatty acids and a short-chain fatty acid. The short - chain fatty acid did not affect the overall consistency of the

Apply siliconcarboxysilane. A white, solid product was obtained.

In the case of the three or four different fatty acids with ^{1 (la bl d)} less than or equal to R ¹ <C14 (carboxy radicals = <C 14), such as caprylic acid, capric acid lauric acid, myristic acid, liquid carboxysilanes have been isolated which are readily soluble in vinyltrimethoxysilane (Carboxysilanes: slightly yellow, slightly viscous and dissolve well in VTMO> 50%).

The carboxy silanes (carboxy radicals> = C 14) prepared from three or four different fatty acids with R ^{1 (la bls d)} greater than or equal to R ¹ > 14 carbon atoms, such as myristic acid, stearic acid, palmitic acid, behenic acid, gave rise to solid, white products that dissolve poorly in VTMO (in VTMO 1%).

Without being bound by theory, it is believed that when three out of four of the carboxy group have more than 14 carbon atoms, the carboxy-silanes produced are solid even if one of these 14 carbon atoms or less (less than 13 carbon atoms). Atoms). Application examples: Carboxysilanes as

 Catalyst Precursor Compounds in Sioplas Process (as Cat-MB)

Execution: extrusion

 Grafting of PE-HD MG9641S from Borealis (M 56/77/08)

with vinyltrimethoxysilane about 90% with peroxide and

processing aids

 The grafting took place on the extruder ZE 25 from Berstorff. Strands were made in the trials. The grafted strands were granulated after extrusion. The granules were packed and sealed in PE-Al-PE bags immediately after granulation. Before welding, the granules were overlaid with nitrogen.

Processing parameter of the grafting reaction on the ZE 25

Temperature profile: - / 150/160/200/200/210/210/210 ° C,

Speed: approx. 100 rpm

 Addition: 1.5 phr vinyltrimethoxysilane 90% (added peroxide, processing aids)

Kneading: Preparation of masterbatches

 Masterbatches with catalyst were prepared. The

Processing took place on the HAAKE laboratory kneader. 49.0 g of PE were kneaded with 1.0 g of catalyst.

processing parameters

 Kneader, hopper, tape tool, tape stripper; filled intake zone,

Speed: 30 rpm, temperature profile: 200 ° C / 5min Preparation of finished mixture of 95% PE-HD vinyl-silane grafted with 5% masterbatch (Cat-MB)

 A mixture of 95% PE-HD silane grafted with 5% masterbatch catalyst (Kat-MB) was kneaded. The processing took place on the HAAKE laboratory kneader. The Kat-MB contains 2% of each active ingredient. The MBs according to the invention

 contain a precursor compound or carboxysilane of the formula I and / or II. Subsequently, it was pressed at 200 ° C into plates and finally crosslinked in a water bath at 80 ° C.

Processing parameters:

 Kneader, hopper; Speed: 30 rpm, temperature profile: 140 ° C / 3min; 2 min at 210 ° C; 210 ° C / 5min; Networking time: Oh, 4h and 22h

Results

Gel [%]

 Gel [%]

 Gel [%] 22h at

Catalyst from Ex. : 4h at 80 ° C

 Oh 80 ° C

 water bath

 water bath

VTC + capric acid Vergleichsbsp. 22,48 35, 82 45, 68

Tegokat 216

 44, 12 61, 37 65, 79 (DOTL)

 Blank value 12, 51 16, 43 33, 60

Table 47

1 = <C14 carboxy radicals: myristic acid, lauric acid,

caprylic

 2> = C14 carboxy radicals: myristic acid, stearic acid,

palmitic

 3 = <C14 carboxy radicals: myristic acid, lauric acid,

Caprylic acid, capric acid

 4 = <C14 carboxy radicals: myristic acid, stearic acid,

Palmitic acid, behenic acid

 5 SiC14 <C14 +> C14 carboxy radicals: caprylic acid,

Palmitic acid, behenic acid

Figure 1: Shows an overview of the gel contents of the various

 Carboxysilanes with three to four different

 Fatty acid residues, [95% PE-HD vinyl-silane grafted with 5% masterbatch / crosslinked in a water bath at 80 ° C.

Figure 2: shows a comparison of the invention

Carboxysilanes with different carboxy radicals on the silane with the carboxysilanes having three or four identical carboxy radicals. Overall, it should be noted that the inventive

Carboxysilanes have catalysed the crosslinking. The solid carboxysilanes, with carboxy radicals greater than 14 C atoms, crosslink better than the liquid carboxysilanes on average

(Carboxy radicals smaller than 14 C atoms) and better than the

Fatty acids and carboxysilanes with 3 identical carboxy radicals.

The carboxy silanes synthesized with CPTCS were not included in the evaluation because in the synthesis the chlorine on the propyl could not be substituted by fatty acid.

Compared to the DOTL approach was the

 Crosslinking speed and the networking of

Carboxysilanes lower. This can be attributed to the overdose of the DOTL.

Claims

claims

1. Composition comprising at least one

 carboxy-functionalized silicon-containing

 Precursor compound of organic acids

 characterized,

 in that it comprises at least one carboxy-functionalized silicon-containing precursor compound of two different organic acids, and

 carboxy-functionalized silicon-containing

 Precursor compound has at least two carboxy groups functionalized with different hydrocarbon radicals and corresponds to the general formula I and / or an oligomeric siloxane derived from the compound of general formula I according to the idealized general formula II

(A) _z SiR ² _x (OR ¹⁾ ₄ - _{(z +} x) (I) (R'O) [(R ¹ 0) ₂ - _(x + z) (R ²⁾ _x Si (A) _z O] _a [Si (A) _z (R ² ) _x (OR ¹ ) ₂ - (x + z) 0] _b R ¹ (II)

- Where in formulas I and II independently z

 equals 0, 1 or 2, x equals 0, 1 or 2, with the proviso that (z + x) is less than or equal to (<) 2

A independently of one another in formulas I and II corresponds to an unsubstituted or substituted hydrocarbon group,

- R ¹ is independently in formula I and in formula II each independently at least two

different carbonyl-R ³ groups, wherein R ³ selected is from a substituted or unsubstituted one

 Hydrocarbon radical with 3 to 45 C atoms,

R ² is independently in formula I and II each independently of one another a linear, branched or cyclic alkyl group having 1 to 24 C atoms or aryl group,

in formula II a is greater than or equal to (>) 1 and b is greater than or equal to (>) 1,

 or it comprises mixtures of these compounds.

2. Composition according to claim 1,

 characterized,

 that in each case in formula I and / or II

 A is a linear, branched or cyclic alkyl,

 alkenyl, aryl, alkylaryl, arylalkylene, cycloalkenylalkylene, haloalkyl and / or acryloyloxyalkyl functional group, in particular a linear, branched and / or cyclic alkyl, cycloalkenylalkylene, arylalkylene, haloalkyl , Alkenyl,

 Alkynyl and / or acryloxyalkyl group having in each case 1 to 18 C atoms and / or an aryl group having 6, 12 or 14 C atoms, preferably a vinyl, propyl, cyclohexenyl-2-ethylene, cyclohexadienyl 2-ethylene or 3-chloropropyl group.

3. Composition according to claim 1 or 2,

 characterized,

 that

(i) each independently in formula I and / or II z is 1 and x is 0 and A is a linear, branched or cyclic alkyl, alkenyl or Haloalkyl group having 1 to 8 carbon atoms or a

Cyclohexenyl-ethylene group and R ¹ independently of one another two or three different carbonyl-R ³

Groups corresponds, wherein independently R ^{3 is} selected from an unsubstituted hydrocarbon radical having 3 to 45 carbon atoms, in particular having 7 to 45 carbon atoms, preferably 7 to 26 carbon atoms or

(ii) each independently of one another in formula I and / or II z is 0 and x is 0 and R ^{1 is} independently two, three or four different carbonyl-R ³ groups, where R ^{3 is} independently selected from an unsubstituted hydrocarbon radical 3 to 45 C atoms, in particular with 7 to 45 C atoms.

4. Composition according to one of claims 1 to 3,

 characterized,

 in each case independently of one another in formula I and / or II

- R ¹ independently corresponds to at least two different carbonyl-R ³ groups, preferably three or four different carbonyl-R ³ groups, wherein in the

different carbonyl R ³ groups

(A) independently at least one first R ³ radical is selected from an unsubstituted

 Hydrocarbon radical having 3 to 14 C-atoms, in particular having 7 to 14 C-atoms, preferably 9 to 13 C-atoms, and

(b) independently at least one further R ³ radical is selected from an unsubstituted radical

 Hydrocarbon radical with 15 to 45 C atoms,

in particular 15 to 26 C atoms, preferably 15 to 20 C atoms.

5. Composition according to one of claims 1 to 4,

 characterized,

 that it comprises substantially carboxy-functionalized silicon-containing precursor compounds of formula I and / or II and in the range of about

 10 ° C to 80 ° C is liquid, in particular between 10 to 60 ° C, preferably between 10 to 40 ° C, especially

 preferably between 10 to 35 ° C.

6. Composition according to one of claims 1 to 5,

 characterized,

 in that the carboxy-functionalized silicon-containing precursor compound of the formula I, formula II or

 Mixtures of these have a solubility of greater than 40% in a hydrocarbon-functionalized alkoxysilane or siloxane, in particular an alkenyl-functionalized alkoxysilane or siloxane.

7. Composition according to one of claims 1 to 6,

 characterized,

 in that it comprises at least one carboxy-functionalized silicon-containing precursor compound of the formula I.

(iii) with z equal to 1 and A is H ₃ C (CH _{2) 2} -, H ₂ C = CH ₂ -, C1CH ₂ (CH _{2) 2} -, C ₆ H ₉ - (CH _{2) 2} -, 3 -C ₆ H ₉ - (CH ₂ ) ₂ -, 2-C ₆ H ₉ - (CH ₂ ) ₂ -, 1 - C ₆ H ₉ - (CH ₂ ) ₂ -, C ₆ H ₈ - (CH ₂ ) ₂ -, l, 3-C ₆ Hg (CH _{2) 2} - or 2,4-C ₆ H ₈ -

(CH ₂ ) ₂ - and OR ¹ in formula I with two or three

various R ¹ selected from -COC ₇ H ₁₅ , -COC ₉ H ₁₉ , -COCnH ₂₃ , -COCi ₃ H ₂₇ , -COC15H31, -COCi ₇ H ₃₅ and -COC ₂ iH ₄₃ , or

(iv) where z is 0 and OR ^{1 is} in formula I with two, three or four different R ¹ selected from -COC ₇ H ₁₅ ,

-COC ₉ H ₁₉ , -COCnH ₂₃ , -COCi ₃ H ₂₇ , -COC15H31, -COCi ₇ H ₃₅ and

-COC ₂ iH ₄₃ , and optionally oligomeric compounds formed from the precursor compounds of the formula I according to the idealized formula II, in particular with a equal to 1 and b equal to 1, or a mixture of these.

8. Composition according to one of claims 1 to 7,

 characterized,

 the carboxy-functionalized silicon-containing precursor compound has at least two with different

 Has hydrocarbon radicals functionalized carboxy groups, and is obtained from the reaction of a

 Halogenosilane of the general formula III,

(A) _z SiR ² x (Hal) ₄ - (z + x) (HI)

- where z is 0, 1 or 2 and x is 0, 1 or 2 where (x + z) is less than or equal to 2, A is as defined above, R ^{2 is} as defined above, and Hal is a halogen selected from chlorine or bromine , having an at least molar stoichiometric ratio with respect to the halogen groups of the formula III with at least two different organic acids of the formula IV, or

 at z equals 1 and x equals 0 with an at least molar stoichiometric ratio with respect to the halogeno groups of formula III with at least two or three different organic acids of formula IV, or

when z is 0 and x is 0 with an at least molar stoichiometric ratio with respect to the halogen groups of the formula III with at least two, three or four different organic acids of formula IV, wherein in the various organic acids of formula IV

LORD ¹ (IV)

- R ¹ independently in formula IV different carbonyl R ³

Corresponds to groups wherein R ^{3 is} independently selected from a substituted or unsubstituted one

 Hydrocarbon radical with 3 to 45 C atoms,

 in particular with 7 to 45 C atoms, preferably 7 to 26 C atoms,

 wherein the reaction is optionally carried out in the presence of an inert solvent which is substantially removed after the reaction.

9. Composition according to one of the claims 1 to 8,

 characterized,

 in that it contains at least one carboxy-functionalized silicon-containing precursor compound of the formula I which is selected from

H ₃ C (CH ₂ ) 2 -Si (OCOC ₇ H ₁₅ ) p (OCOCiiH ₂₃ ) p (OCOC ₁₃ H ₂₇ ) p,

H ₃ C (CH ₂ ) 2 -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P ,

H ₂ C = CH ₂ -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p,

H ₂ C = CH ₂ -Si (OCOC ₁₃ H ₂₇ ) _p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _p .

C ₆ H ₉ - (CH ₂ ) ₂ -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p _,

C ₆ H ₉ - (CH ₂ ) ₂ -Si (OCOC ₁₃ H ₂₇ ) _p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _P ,

C1CH ₂ (CH _{2) 2} Si (OCOC ₇ H ₁₅₎ p (OCOCnH _{23) P} (OCOC ₁₃ H _{27) P,}

CICH2 _(CH2) 2-Si (OCOC ₁₃ H ₂₇₎ p (OCOC ₁₅ H ₃₁₎ p (OCOC ₁₇ H _{35) P,}

(H ₁₉ C ₉ OCO) p (CICH ₂ (CH ₂ ) 2) Si (OCOC ₇ H ₁₅ ) p (OCOCnH ₂₃ ) _P (OCOC ₁₃ H ₂₇ ) _P , (H43C21OCO) p (CICH2 (CH _{2) 2} Si (OCOC ₁₃ H ₂₇₎ p (OCOC ₁₅ H ₃ i) p (OCOC ₁₇ H _{35) P,}

(H ₁₉ C ₉ OCO) p (CICH ₂ (CH ₂ ) 2) Si (OCOC ₇ H ₁₅ ) p (OCOCnH ₂₃ ) _P (OCOC ₁₃ H ₂₇ ) _P ,

(H ₁₉ C ₉ OCO) _p Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p,

(H ₄₃ C ₂ iOCO) _p Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) _p (OCOC ₁₇ H ₃₅ ) _P

(H ₃₃ C ₁₆ ) -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p

(H ₃₃ C ₁₆ ) -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P ,

(C ₁₇ H ₈₎ Si (OCOC ₇ H ₁₅₎ p (OCOC11H23) p (OCOC ₁₃ H ₂₇₎ p

(H ₁₇ C ₈ ) -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P ,

(H ₉ C ₄ ) -Si (OCOC ₇ H ₁₅ ) p (OCOC 11 H 23) p (OCOC ₁₃ H ₂₇ ) p

(H ₉ C ₄ ) -Si (OCOC ₁₃ H ₂₇ ) p (OCOC ₁₅ H ₃₁ ) p (OCOC ₁₇ H ₃₅ ) _P , each with p equal to 0, 1, 2 or 3, with the proviso that at least two different carboxy groups p is 1 and the sum of all p per silicon containing

 Precursor compound is 3, when in formula I z = 1 and the sum of all p is 4 in tetra-carboxy

 functionalized precursor compounds of formula I with z = 0, and optionally corresponding oligomeric compounds of these precursor compounds or a

 Mix this.

10. The composition according to any one of claims 1 to 9,

 characterized,

 that they are applied to a substrate in one

 Embedded carrier material and / or encapsulated.

11. A composition according to any one of claims 1 to 10, suitable for crosslinking of thermoplastic base polymers, characterized in that they

at least one silicon-containing precursor compound of at least two different organic acids of the general formula I and / or II correspondingly above Definition as component-A includes, and

 optionally as component B, a radical generator and

optionally, as component C, an organofunctional silane compound,

 in particular of the formula V,

(B) _b SiR ⁴ _c (OR ⁵ ) ₃ -dc (V)

where, independently of one another, d is 0, 1, 2 or 3 and c is 0, 1, 2

 or 3, with the proviso that in formula V c + d is less than or equal to (<) 3,

 - with B independently of each other for a monovalent one

unsaturated hydrocarbon group in formula V, in particular (R ⁷ ) 2C = C (R ⁷ ) -E _q -, wherein R ^{7 are the} same or different and R ^{7 is} independently a hydrogen atom, methyl or phenyl group, the group E a group from the group -CH ₂ -, - (CH ₂ ) 2 -, ^_ (CH ₂ ) 3, - 0 (0) C (CH ₂ ) ₃ - or -C (O) O- (CH ₂ ) ₃ - represents q is 0 or 1, preferably a vinyl group,

R ⁵ is independently methyl, ethyl, n-propyl and / or iso-propyl,

R ⁴ is independently a substituted or unsubstituted one

 Hydrocarbon group, in particular an alkyl group having 1 to 16 C

Atoms or an aryl group.

Silicon-containing precursor compound of general formula I and / or II as defined in any one of claims 1 to 11. A process for preparing a composition according to any one of claims 1 to 11, comprising at least one

carboxy-functionalized silicon-containing

Precursor compound of an organic acid having at least two with different hydrocarbon radicals

functionalized carboxy groups,

by a halosilane of the formula III

(A) _z SiR ² x (Hal) ₄ - (z + x) (HD

- where z is 0, 1 or 2, x is 0, 1 or 2 and (z + x) is less than or equal to (<) 2,

 - A is independently an unsubstituted or substituted

 Hydrocarbon group,

R ^{2 is} independently an unsubstituted linear or branched

 Alkyl group having 1 to 24 carbon atoms or aryl group and shark each independently a halogen group selected from chlorine or bromine are reacted with at least two different organic acids of formula IV,

- wherein in the different organic acids of formula IV

LORD ¹ (IV)

R ¹ independently corresponds to a carbonyl-R ³ group, wherein R ^{3 is} independently selected from a substituted or unsubstituted

Hydrocarbon radical with 3 to 45 C atoms, and the organic acids are optionally present in at least a molar stoichiometric ratio to the halogen groups of the formula III, optionally in

 Presence of an inert solvent.

14. The method according to claim 13,

 characterized,

 that the various organic acids of formula IV with each other in the ratio of 10: 1 to 1: 10

 are used, preferably the different acids of formula IV are used approximately equimolar,

15. The method according to claim 13 or 14,

 characterized,

 that if in formula III

 (v) z is 1 and x is 0 and A is one

 unsubstituted or substituted

 Hydrocarbon group correspond to two or three different organic acids of the formula IV at least in the molar stoichiometric ratio with respect to the halogen groups of the formula III or, if

(vi) z is 0 and x is 0, two, three or four different organic acids of formula IV are reacted at least in the molar stoichiometric ratio with respect to the halogen groups of the formula III.

16. The method according to any one of claims 13 to 15,

 characterized,

 that a compound of general formula III

v) where z is 1 and A is H ₃ C (CH ₂ ) 2 ^_ , (H 33 C 16) -,

 especially n- / iso- (H33C16) -, (HivCs) -, (H9C4) -,

H2C = CH 2 ^_, CICH2 (CH ₂₎ 2 ~ r C6H9- _(CH2) 2 ~ r 3-C6H9- (CH2) 2 ^_ r ^~ C6H9- _(CH2) 2 ~ rl ^_ C6Hg- (CH ₂₎ 2 ~ r ^ C6 - (CH2) 2 ^_ r ^ 1.3 to 06 -

(CH ₂ ) ₂ -, or 2,4-C ₆ H ₈ - (CH ₂ ) ₂ - and

is reacted with at least two or three different organic acids of the formula IV, wherein R ^{1 is} independently selected from

-COC7H15, -COC9H19, -COCnH23, -COCl ₃ H27, -COC15H31,

-COCi ₇ H ₃₅ and -COC ₂ iH ₄₃ , or

(vi) when z is 0, it is reacted with at least two, three or four different organic acids of formula IV, wherein R ^{1 is} independently selected

-COC7H15, -COC9H19, -COCnH23, -COCl ₃ H27, -COC15H31 -

COCi ₇ H ₃₅ and -C ₂ iH ₄₃ .

17. Use of a composition or a compound of the formula I or II according to one of claims 1 to 16

 as a precursor compound of a silane hydrolysis catalyst and / or as a silanol condensation catalyst in which

 Preparation of a silicon-containing polymer,

 Polymer compounds, an unfilled crosslinked polymer and / or a filled crosslinked polymer, in a monosil, sioplas and / or co-polymerization process, to produce unfilled Si-crosslinked polymer compounds, to produce filled Si-crosslinked polymer compounds; correspondingly filled Si-crosslinked or unfilled Si-crosslinked polymers based on

thermoplastic base polymers; together with one organofunctional silane compound; together with an organofunctional silane compound, preferably of formula V as defined above, for grafting onto a base polymer, for co-polymerizing with a monomer and / or prepolymer of the base polymer, optionally in the presence of a free radical generator; in the manufacture of articles, moldings, cables or pipes, together with other silanol condensation catalysts.

Masterbatch containing a composition or a

A compound of formula I or II according to any one of claims 1 to 16, in particular for the crosslinking of thermoplastic base polymers, characterized in that it comprises at least one silicon-containing precursor compound of a

organic acid of formula I and / or formula II and a thermoplastic base polymer, a silane-grafted base polymer, a silane-co-polymerized base polymer, a monomer of these base polymers, a prepolymer of these base polymers and / or mixtures thereof, and

optionally comprising a free radical generator.